WO2020021733A1 - Slurry, screening method, and polishing method - Google Patents

Slurry, screening method, and polishing method Download PDF

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Publication number
WO2020021733A1
WO2020021733A1 PCT/JP2018/035485 JP2018035485W WO2020021733A1 WO 2020021733 A1 WO2020021733 A1 WO 2020021733A1 JP 2018035485 W JP2018035485 W JP 2018035485W WO 2020021733 A1 WO2020021733 A1 WO 2020021733A1
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Prior art keywords
slurry
mass
particles
abrasive grains
metal
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PCT/JP2018/035485
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French (fr)
Japanese (ja)
Inventor
野村　理行
友洋 岩野
貴彬 松本
智康 長谷川
友美 久木田
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日立化成株式会社
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Priority to SG11202100636YA priority Critical patent/SG11202100636YA/en
Priority to CN201880097068.2A priority patent/CN112930585A/en
Priority to KR1020217003393A priority patent/KR102580184B1/en
Priority to US17/263,089 priority patent/US20210309884A1/en
Priority to JP2020532134A priority patent/JP6989020B2/en
Priority to TW108126169A priority patent/TWI835824B/en
Publication of WO2020021733A1 publication Critical patent/WO2020021733A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1436—Composite particles, e.g. coated particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers
    • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L22/00—Testing or measuring during manufacture or treatment; Reliability measurements, i.e. testing of parts without further processing to modify the parts as such; Structural arrangements therefor
    • H01L22/20—Sequence of activities consisting of a plurality of measurements, corrections, marking or sorting steps
    • H01L22/26—Acting in response to an ongoing measurement without interruption of processing, e.g. endpoint detection, in-situ thickness measurement
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C01F17/235—Cerium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Definitions

  • the polishing rate of the insulating material can be improved, and the insulating material can be polished at a high polishing rate.
  • the weight average molecular weight in the present specification can be measured, for example, by gel permeation chromatography (GPC) using a standard polystyrene calibration curve under the following conditions.
  • Equipment used Hitachi L-6000 type [manufactured by Hitachi, Ltd.]
  • Flow rate 1.75 mL / min
  • Detector L-3300RI [manufactured by Hitachi, Ltd.]
  • Cerium hydroxide can be produced by reacting a cerium salt with an alkali source (base).
  • Cerium hydroxide can be prepared by mixing a cerium salt and an alkaline liquid (eg, an alkaline aqueous solution).
  • Cerium hydroxide can be obtained by mixing a cerium salt solution (for example, a cerium salt aqueous solution) and an alkali solution.
  • the cerium salt include Ce (NO 3 ) 4 , Ce (SO 4 ) 2 , Ce (NH 4 ) 2 (NO 3 ) 6 , Ce (NH 4 ) 4 (SO 4 ) 4 and the like.
  • Examples of the material having a carboxyl group include monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and valeric acid; hydroxy acids such as lactic acid, malic acid, and citric acid; and dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, and maleic acid.
  • Monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and valeric acid
  • hydroxy acids such as lactic acid, malic acid, and citric acid
  • dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, and maleic acid.
  • Polycarboxylic acids such as polyacrylic acid and polymaleic acid
  • amino acids such as arginine, histidine and lysine.
  • the lower limit of the pH of the slurry according to this embodiment is preferably 2.0 or more, more preferably 2.5 or more, still more preferably 2.8 or more, from the viewpoint of further improving the polishing rate of the insulating material.
  • the above is particularly preferred.
  • the lower limit of the pH may be not less than 3.2, not less than 3.5, not less than 4.0, not less than 4.2, and not less than 4.3.
  • the upper limit of the pH is preferably 7.0 or less from the viewpoint of further improving the storage stability of the slurry.
  • the upper limit of the pH may be 6.5 or less, may be 6.0 or less, may be 5.0 or less, may be 4.8 or less, may be 4.7 or less, It may be 4.6 or less, may be 4.5 or less, and may be 4.4 or less. From the above viewpoint, the pH is more preferably from 2.0 to 7.0.
  • the pH of the slurry is defined as the pH at a liquid temperature of 25 ° C.
  • the pH of the slurry according to the present embodiment can be measured with a pH meter (for example, model number PHL-40 manufactured by Toa DKK Ltd.). Specifically, for example, after two-point calibration of a pH meter using a phthalate pH buffer (pH: 4.01) and a neutral phosphate pH buffer (pH: 6.86) as a standard buffer, The electrode of the pH meter is put in the slurry, and the value is measured after 2 minutes or more have passed and stabilized. The temperature of both the standard buffer and the slurry is 25 ° C.
  • the slurry screening method may include, after the measuring step, a determining step of determining the ratio of the valence obtained in the measuring step.
  • a determining step of determining the ratio of the valence obtained in the measuring step for example, a slurry that gives a valence ratio of 0.13 or more is selected.
  • cerium oxide slurry An appropriate amount of cerium oxide slurry was charged into Beckman Coulter Co., Ltd. trade name: DelsaNano @ C, and the measurement was performed twice at 25 ° C. The average value of the indicated zeta potential was obtained as the zeta potential.
  • the zeta potential of the cerium oxide particles in the cerium oxide slurry was -55 mV.

Abstract

This slurry contains abrasive grains and a liquid medium, wherein the abrasive grains contain at least one type of metal compound selected from the group consisting of metal oxides and metal hydroxides, the metal compound contains a metal that can take multiple valences, and, when the abrasive grains contact the polishing surface by the slurry contacting the polishing surface, X-ray photoelectron spectroscopy of the slurry yields 0.13 or higher as the ratio of the aforementioned metal that has the lowest of the multiple valences.

Description

スラリ及びそのスクリーニング方法、並びに、研磨方法Slurry, screening method thereof, and polishing method
　本発明は、スラリ及びそのスクリーニング方法、並びに、研磨方法に関する。 (4) The present invention relates to a slurry, a screening method thereof, and a polishing method.
　近年の半導体素子の製造工程では、高密度化及び微細化のための加工技術の重要性がますます高まっている。加工技術の一つであるＣＭＰ（ケミカル・メカニカル・ポリッシング：化学機械研磨）技術は、半導体素子の製造工程において、シャロートレンチ分離（シャロー・トレンチ・アイソレーション。以下「ＳＴＩ」という。）の形成、プリメタル絶縁材料又は層間絶縁材料の平坦化、プラグ又は埋め込み金属配線の形成等に必須の技術となっている。 で は In the semiconductor device manufacturing process in recent years, processing technology for high density and miniaturization has become more and more important. A CMP (Chemical Mechanical Polishing) technique, which is one of the processing techniques, forms a shallow trench isolation (shallow trench isolation; hereinafter, referred to as "STI") in a semiconductor device manufacturing process. It is an indispensable technique for flattening a premetal insulating material or an interlayer insulating material, forming a plug or a buried metal wiring, and the like.
　最も多用されている研磨液としては、例えば、砥粒として、ヒュームドシリカ、コロイダルシリカ等のシリカ（酸化珪素）粒子を含むシリカ系研磨液が挙げられる。シリカ系研磨液は、汎用性が高いことが特徴であり、砥粒含有量、ｐＨ、添加剤等を適切に選択することで、絶縁材料及び導電材料を問わず幅広い種類の材料を研磨できる。 研磨 The most frequently used polishing liquid is, for example, a silica-based polishing liquid containing silica (silicon oxide) particles such as fumed silica and colloidal silica as abrasive grains. The silica-based polishing liquid is characterized by being highly versatile, and can appropriately polish a wide variety of materials irrespective of insulating materials and conductive materials by appropriately selecting the abrasive content, pH, additives, and the like.
　一方で、主に酸化珪素等の絶縁材料を対象とした研磨液として、セリウム化合物粒子を砥粒として含む研磨液の需要も拡大している。例えば、セリウム酸化物粒子を砥粒として含むセリウム酸化物系研磨液は、シリカ系研磨液よりも低い砥粒含有量でも高速に酸化珪素を研磨できる（例えば、下記特許文献１及び２参照）。 On the other hand, as a polishing liquid mainly for an insulating material such as silicon oxide, the demand for a polishing liquid containing cerium compound particles as abrasive grains is also increasing. For example, a cerium oxide-based polishing liquid containing cerium oxide particles as abrasive grains can polish silicon oxide at high speed even with a lower abrasive content than a silica-based polishing liquid (for example, see Patent Documents 1 and 2 below).
特開平１０－１０６９９４号公報JP-A-10-106994 特開平０８－０２２９７０号公報JP-A-08-022970
　ところで、近年、デバイスのセル部を縦方向に積層させる３Ｄ－ＮＡＮＤデバイスが台頭してきている。本技術では、セル形成時の絶縁材料の段差が従来のプレーナ型と比べて数倍高くなっている。それに伴い、デバイス製造のスループットを維持するためには、前記のとおりの高い段差をＣＭＰ工程等において素早く解消する必要があり、絶縁材料の研磨速度を向上させる必要がある。 By the way, in recent years, 3D-NAND devices in which the cell portions of the devices are stacked in the vertical direction have emerged. In the present technology, the step of the insulating material at the time of forming the cell is several times higher than that of the conventional planar type. Accordingly, in order to maintain the device manufacturing throughput, it is necessary to quickly eliminate the high steps as described above in the CMP process or the like, and it is necessary to improve the polishing rate of the insulating material.
　本発明は、前記課題を解決しようとするものであり、絶縁材料の研磨速度を向上させることが可能なスラリを提供することを目的とする。また、本発明は、絶縁材料の研磨速度を向上させることが可能なスラリを選定できるスラリのスクリーニング方法を提供することを目的とする。さらに、本発明は、絶縁材料の研磨速度を向上させることが可能な研磨方法を提供することを目的とする。 The present invention has been made to solve the above-described problem, and has as its object to provide a slurry capable of improving a polishing rate of an insulating material. Another object of the present invention is to provide a slurry screening method capable of selecting a slurry capable of improving a polishing rate of an insulating material. Still another object of the present invention is to provide a polishing method capable of improving a polishing rate of an insulating material.
　本発明の一側面に係るスラリは、砥粒及び液状媒体を含有するスラリであって、前記砥粒が、金属酸化物及び金属水酸化物からなる群より選ばれる少なくとも一種の金属化合物を含み、前記金属化合物が、複数の価数を取り得る金属を含み、前記スラリが、当該スラリを被研磨面に接触させることにより前記砥粒を前記被研磨面に接触させたときに、前記金属の前記複数の価数の中で最も小さい価数の割合としてＸ線光電子分光法において０．１３以上を与える。 The slurry according to one aspect of the present invention is a slurry containing abrasive grains and a liquid medium, wherein the abrasive grains include at least one metal compound selected from the group consisting of metal oxides and metal hydroxides, The metal compound contains a metal capable of taking a plurality of valences, and the slurry, when the abrasive grains are brought into contact with the surface to be polished by contacting the slurry with the surface to be polished, In the X-ray photoelectron spectroscopy, 0.13 or more is given as the ratio of the smallest valence among a plurality of valences.
　このようなスラリによれば、絶縁材料の研磨速度を向上させることが可能であり、絶縁材料を高い研磨速度で研磨できる。 According to such a slurry, the polishing rate of the insulating material can be improved, and the insulating material can be polished at a high polishing rate.
　本発明の他の一側面に係るスラリのスクリーニング方法は、砥粒及び液状媒体を含有するスラリを被研磨面に接触させることにより前記砥粒を前記被研磨面に接触させる工程と、前記被研磨面に前記砥粒が接触した状態で、前記砥粒に含まれる金属の価数をＸ線光電子分光法により測定する測定工程と、を備え、前記砥粒が、金属酸化物及び金属水酸化物からなる群より選ばれる少なくとも一種の金属化合物を含み、前記金属化合物が、複数の価数を取り得る金属を含み、前記測定工程において、前記金属の前記複数の価数の中で最も小さい価数の割合を得る。 A method for screening a slurry according to another aspect of the present invention includes a step of contacting the abrasive grains with the surface to be polished by contacting a slurry containing abrasive grains and a liquid medium with the surface to be polished; A step of measuring the valence of metal contained in the abrasive grains by X-ray photoelectron spectroscopy in a state where the abrasive grains are in contact with a surface, wherein the abrasive grains are a metal oxide and a metal hydroxide. At least one metal compound selected from the group consisting of: the metal compound includes a metal capable of taking a plurality of valences, and in the measurement step, the smallest valence among the plurality of valences of the metal To get the percentage.
　このようなスラリのスクリーニング方法によれば、絶縁材料の研磨速度を向上させることが可能なスラリを選定できる。 According to such a slurry screening method, a slurry capable of improving the polishing rate of the insulating material can be selected.
　本発明の他の一側面に係る研磨方法は、上述のスラリのスクリーニング方法の前記測定工程において得られる前記価数の割合として０．１３以上を与えるスラリを用いて前記被研磨面を研磨する工程を備える。 A polishing method according to another aspect of the present invention includes a step of polishing the surface to be polished using a slurry that gives a valence ratio of 0.13 or more obtained in the measurement step of the slurry screening method described above. Is provided.
　このような研磨方法によれば、絶縁材料の研磨速度を向上させることが可能であり、絶縁材料を高い研磨速度で研磨できる。 According to such a polishing method, the polishing rate of the insulating material can be improved, and the insulating material can be polished at a high polishing rate.
　本発明によれば、絶縁材料の研磨速度を向上させることが可能なスラリを提供することができる。また、本発明によれば、絶縁材料の研磨速度を向上させることが可能なスラリを選定できるスラリのスクリーニング方法を提供することができる。さらに、本発明によれば、絶縁材料の研磨速度を向上させることが可能な研磨方法を提供することができる。 According to the present invention, it is possible to provide a slurry capable of improving a polishing rate of an insulating material. Further, according to the present invention, it is possible to provide a slurry screening method capable of selecting a slurry capable of improving a polishing rate of an insulating material. Further, according to the present invention, it is possible to provide a polishing method capable of improving a polishing rate of an insulating material.
　本発明によれば、絶縁材料を含む被研磨面の研磨へのスラリの使用を提供することができる。本発明によれば、半導体素子の製造技術である基体表面の平坦化工程へのスラリの使用を提供することができる。本発明によれば、ＳＴＩ絶縁材料、プリメタル絶縁材料又は層間絶縁材料の平坦化工程へのスラリの使用を提供することができる。 According to the present invention, it is possible to provide use of a slurry for polishing a surface to be polished including an insulating material. According to the present invention, it is possible to provide the use of the slurry in the step of flattening the surface of the substrate, which is a technique for manufacturing a semiconductor device. According to the present invention, it is possible to provide the use of the slurry in the step of planarizing an STI insulating material, a pre-metal insulating material or an interlayer insulating material.
　以下、本発明の実施形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
＜定義＞
　本明細書において、「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。本明細書に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値と任意に組み合わせることができる。本明細書に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。「Ａ又はＢ」とは、Ａ及びＢのどちらか一方を含んでいればよく、両方とも含んでいてもよい。本明細書に例示する材料は、特に断らない限り、１種を単独で又は２種以上を組み合わせて用いることができる。本明細書において、組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。 <Definition>
In the present specification, a numerical range indicated by using “to” indicates a range including numerical values described before and after “to” as a minimum value and a maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit or the lower limit of a numerical range in one step can be arbitrarily combined with the upper limit or the lower limit of a numerical range in another step. In the numerical ranges described in this specification, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment. “A or B” may include one of A and B, and may include both. The materials exemplified in the present specification can be used alone or in combination of two or more, unless otherwise specified. In the present specification, the content of each component in the composition, if there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the total amount of the plurality of substances present in the composition Means The term "step" is included in the term as well as an independent step, even if it is not clearly distinguishable from other steps, provided that the intended action of that step is achieved.
　後述するように、本実施形態に係るスラリは砥粒（abrasive　grain）を含有する。砥粒は、「研磨粒子」（abrasive　particle）ともいわれるが、本明細書では「砥粒」という。砥粒は、一般的には固体粒子であって、研磨時に、砥粒が有する機械的作用（物理的作用）、及び、砥粒（主に砥粒の表面）の化学的作用によって、除去対象物が除去（remove）されると考えられるが、これに限定されない。 よ う As will be described later, the slurry according to the present embodiment contains abrasive grains. The abrasive grains are also referred to as “abrasive particles”, but are referred to herein as “abrasive grains”. Abrasive grains are generally solid particles, and are removed by a mechanical action (physical action) of the abrasive grains during polishing and a chemical action of the abrasive grains (mainly, the surface of the abrasive grains). It is contemplated, but not limited to, that the object is removed.
　本明細書において、「研磨液」（polishing　liquid、abrasive）とは、研磨時に被研磨面に触れる組成物として定義される。「研磨液」という語句自体は、研磨液に含有される成分を何ら限定しない。 に お い て In the present specification, “polishing liquid” (abrasive) is defined as a composition that comes into contact with a surface to be polished during polishing. The phrase "polishing liquid" itself does not limit the components contained in the polishing liquid at all.
　本明細書における重量平均分子量は、例えば、標準ポリスチレンの検量線を用いてゲルパーミエーションクロマトグラフィー法（ＧＰＣ）により下記の条件で測定することができる。
　使用機器：日立Ｌ－６０００型［株式会社日立製作所製］
　カラム：ゲルパックＧＬ－Ｒ４２０＋ゲルパックＧＬ－Ｒ４３０＋ゲルパックＧＬ－Ｒ４４０［日立化成株式会社製　商品名、計３本］
　溶離液：テトラヒドロフラン
　測定温度：４０℃
　流量：１．７５ｍＬ／ｍｉｎ
　検出器：Ｌ－３３００ＲＩ［株式会社日立製作所製］ The weight average molecular weight in the present specification can be measured, for example, by gel permeation chromatography (GPC) using a standard polystyrene calibration curve under the following conditions.
Equipment used: Hitachi L-6000 type [manufactured by Hitachi, Ltd.]
Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 [Hitachi Chemical Co., Ltd. product name, total of 3]
Eluent: tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 1.75 mL / min
Detector: L-3300RI [manufactured by Hitachi, Ltd.]
＜スラリ＞
　本実施形態に係るスラリは、必須成分として砥粒と液状媒体とを含有する。本実施形態に係るスラリは、例えば、研磨液（ＣＭＰ研磨液）として用いることができる。 <Slurry>
The slurry according to the present embodiment contains abrasive grains and a liquid medium as essential components. The slurry according to the present embodiment can be used, for example, as a polishing liquid (CMP polishing liquid).
　砥粒は、金属酸化物及び金属水酸化物からなる群より選ばれる少なくとも一種の金属化合物を含み、前記金属化合物が、複数の価数（原子価）を取り得る金属を含む。また、本実施形態に係るスラリは、当該スラリを被研磨面に接触させることにより砥粒を被研磨面に接触させたときに、上述の金属の複数の価数の中で最も小さい価数の割合としてＸ線光電子分光法（ＸＰＳ：Ｘ－ｒａｙ　Ｐｈｏｔｏｅｌｅｃｔｒｏｎ　Ｓｐｅｃｔｒｏｓｃｏｐｙ）において０．１３以上を与える。 The abrasive grains include at least one metal compound selected from the group consisting of metal oxides and metal hydroxides, and the metal compound includes a metal capable of taking a plurality of valences (valences). Further, the slurry according to the present embodiment, when the abrasive grains are brought into contact with the surface to be polished by contacting the slurry with the surface to be polished, the smallest valence among the plurality of valences of the metal described above. In X-ray photoelectron spectroscopy (XPS: X-ray @ Photoelectron @ Spectroscopy), 0.13 or more is given as a ratio.
　本実施形態に係るスラリを用いることにより絶縁材料（例えば酸化珪素）の研磨速度を向上させることができる。このように絶縁材料の研磨速度が向上する理由としては、例えば、酸化珪素を一例として下記の理由が挙げられる。但し、理由は下記に限定されない。 研磨 By using the slurry according to the present embodiment, the polishing rate of the insulating material (for example, silicon oxide) can be improved. The reason why the polishing rate of the insulating material is improved in this manner is as follows, for example, with silicon oxide as an example. However, the reason is not limited to the following.
　すなわち、酸化珪素の研磨に際しては、砥粒中の金属原子と酸化珪素の珪素原子とが酸素原子を介して結合する第１段階（例えば、金属原子がセリウムである場合にＣｅ－Ｏ－Ｓｉ結合が生成する段階）と、金属原子－酸素原子－珪素原子の結合を保持したまま、被研磨面における珪素原子と他の酸素原子との結合が切断されることにより珪素原子が被研磨面から除去される第２段階とが生じる。そして、砥粒が酸化珪素に接触した後に、砥粒中の金属の価数のうち、最も小さい価数の割合が大きいほど上記第１段階が進行しやすいことから酸化珪素の研磨が全体として進行しやすい。このような観点から、砥粒に含まれる金属の複数の価数の中で最も小さい価数の割合が上記所定値以上である場合には、上記第１段階が進行しやすいことから酸化珪素の研磨が全体として進行しやすい。以上より、酸化珪素の研磨速度が向上する。 That is, in the polishing of silicon oxide, the first step in which metal atoms in abrasive grains and silicon atoms of silicon oxide are bonded via oxygen atoms (for example, when the metal atoms are cerium, Ce—O—Si bonding Is generated), and the silicon atoms are removed from the surface to be polished by cutting the bonds between the silicon atoms and other oxygen atoms on the surface to be polished while maintaining the bond of metal atom-oxygen atom-silicon atom. A second stage occurs. Then, after the abrasive grains come into contact with silicon oxide, the first stage is more likely to proceed as the ratio of the smallest valence among the valences of the metal in the abrasive grains increases, so that the polishing of silicon oxide proceeds as a whole. It's easy to do. From such a viewpoint, when the ratio of the smallest valence among the plurality of valences of the metal contained in the abrasive grains is equal to or more than the above-described predetermined value, the first stage is likely to proceed, and thus the silicon oxide Polishing easily proceeds as a whole. As described above, the polishing rate of silicon oxide is improved.
（砥粒）
　本実施形態に係るスラリの砥粒は、金属酸化物及び金属水酸化物からなる群より選ばれる少なくとも一種の金属化合物を含み、前記金属化合物が、複数の価数を取り得る金属（以下、「金属Ｍ」という）を含む。すなわち、砥粒は、金属Ｍを含む酸化物、及び、金属Ｍを含む水酸化物からなる群より選ばれる少なくとも一種を含む。 (Abrasive)
The abrasive grains of the slurry according to the present embodiment include at least one metal compound selected from the group consisting of a metal oxide and a metal hydroxide, and the metal compound has a plurality of valences (hereinafter, “metal”). Metal M "). That is, the abrasive grains include at least one selected from the group consisting of an oxide containing the metal M and a hydroxide containing the metal M.
　金属Ｍは、絶縁材料の研磨速度が更に向上する観点から、珪素（Ｓｉ）、バナジウム（Ｖ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）、銀（Ａｇ）、インジウム（Ｉｎ）、スズ（Ｓｎ）、希土類元素（希土類金属元素）、タングステン（Ｗ）、及び、ビスマス（Ｂｉ）からなる群より選ばれる少なくとも一種を含むことが好ましい。金属Ｍは、絶縁材料の研磨速度が更に向上する観点から、希土類元素として、スカンジウム（Ｓｃ）及びランタノイドからなる群より選ばれる少なくとも一種を含むことが好ましい。金属Ｍは、絶縁材料の研磨速度が更に向上する観点から、ランタノイドとして、セリウム（Ｃｅ）、プラセオジム（Ｐｒ）、ユウロピウム（Ｅｕ）、テルビウム（Ｔｂ）、及び、イッテルビウム（Ｙｂ）からなる群より選ばれる少なくとも一種を含むことが好ましい。金属Ｍは、絶縁材料の研磨速度が更に向上する観点から、希土類元素を含むことが好ましく、ランタノイドを含むことがより好ましく、セリウムを含むことが更に好ましい。 The metal M is silicon (Si), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu) from the viewpoint of further improving the polishing rate of the insulating material. , Silver (Ag), indium (In), tin (Sn), a rare earth element (rare earth metal element), tungsten (W), and bismuth (Bi). The metal M preferably contains at least one selected from the group consisting of scandium (Sc) and lanthanoids as a rare earth element from the viewpoint of further improving the polishing rate of the insulating material. The metal M is selected from the group consisting of cerium (Ce), praseodymium (Pr), europium (Eu), terbium (Tb), and ytterbium (Yb) as lanthanoids from the viewpoint of further improving the polishing rate of the insulating material. It is preferable to include at least one of these. From the viewpoint of further improving the polishing rate of the insulating material, the metal M preferably contains a rare earth element, more preferably contains a lanthanoid, and further preferably contains cerium.
　砥粒は、絶縁材料の研磨速度が更に向上する観点から、セリウム酸化物（セリウムを含む酸化物）、及び、セリウム水酸化物（セリウムを含む水酸化物）からなる群より選ばれる少なくとも一種を含むことが好ましい。 From the viewpoint of further improving the polishing rate of the insulating material, the abrasive grains include at least one selected from the group consisting of cerium oxide (oxide containing cerium), and cerium hydroxide (hydroxide containing cerium). It is preferred to include.
　セリウム酸化物としては、４価セリウムを含む酸化物（酸化セリウム（ＩＶ）、セリア、ＣｅＯ２）、３価セリウムを含む酸化物（酸化セリウム（ＩＩＩ）、Ｃｅ２Ｏ３）等が挙げられる。セリウム酸化物が３価セリウム及び４価セリウムを含む場合、金属Ｍの複数の価数の中で最も小さい価数は３価である。 Examples of the cerium oxide include oxides containing tetravalent cerium (cerium (IV) oxide, ceria, CeO 2 ), and oxides containing trivalent cerium (cerium (III) oxide, Ce 2 O 3 ). When the cerium oxide contains trivalent cerium and tetravalent cerium, the smallest valence among the plurality of valences of the metal M is trivalent.
　セリウム酸化物は、例えば、炭酸塩、硝酸塩、硫酸塩、シュウ酸塩等のセリウム塩を酸化させることにより作製できる。酸化の方法としては、セリウム塩を６００～９００℃程度で焼成する焼成法；過酸化水素等の酸化剤を用いてセリウム塩を酸化する化学的酸化法などが挙げられる。 Cerium oxide can be produced by, for example, oxidizing a cerium salt such as a carbonate, a nitrate, a sulfate, and an oxalate. Examples of the oxidation method include a firing method in which a cerium salt is fired at about 600 to 900 ° C .; a chemical oxidation method in which the cerium salt is oxidized using an oxidizing agent such as hydrogen peroxide.
　セリウム水酸化物は、例えば、セリウムイオンと、少なくとも１つの水酸化物イオン（ＯＨ－）とを含む化合物である。セリウム水酸化物は、水酸化物イオン以外の陰イオン（例えば、硝酸イオンＮＯ３ －及び硫酸イオンＳＯ４ ２－）を含んでいてもよい。例えば、セリウム水酸化物は、セリウムイオンに結合した陰イオン（例えば、硝酸イオンＮＯ３ －及び硫酸イオンＳＯ４ ２－）を含んでいてもよい。 Cerium hydroxide is, for example, a compound containing cerium ions and at least one hydroxide ion (OH − ). Cerium hydroxide may include anions other than hydroxide ions (eg, nitrate ions NO 3 − and sulfate ions SO 4 2− ). For example, cerium hydroxide may include anions (eg, nitrate ions NO 3 − and sulfate ions SO 4 2− ) bonded to cerium ions.
　セリウム水酸化物は、セリウム塩と、アルカリ源（塩基）とを反応させることにより作製できる。セリウム水酸化物は、セリウム塩とアルカリ液（例えばアルカリ水溶液）とを混合することにより作製できる。セリウム水酸化物は、セリウム塩溶液（例えばセリウム塩水溶液）とアルカリ液とを混合することにより得ることができる。セリウム塩としては、Ｃｅ（ＮＯ３）４、Ｃｅ（ＳＯ４）２、Ｃｅ（ＮＨ４）２（ＮＯ３）６、Ｃｅ（ＮＨ４）４（ＳＯ４）４等が挙げられる。 Cerium hydroxide can be produced by reacting a cerium salt with an alkali source (base). Cerium hydroxide can be prepared by mixing a cerium salt and an alkaline liquid (eg, an alkaline aqueous solution). Cerium hydroxide can be obtained by mixing a cerium salt solution (for example, a cerium salt aqueous solution) and an alkali solution. Examples of the cerium salt include Ce (NO 3 ) 4 , Ce (SO 4 ) 2 , Ce (NH 4 ) 2 (NO 3 ) 6 , Ce (NH 4 ) 4 (SO 4 ) 4 and the like.
　セリウム水酸化物の製造条件等に応じて、セリウムイオン、１～３個の水酸化物イオン（ＯＨ－）及び１～３個の陰イオン（Ｘｃ－）からなるＣｅ（ＯＨ）ａＸｂ（式中、ａ＋ｂ×ｃ＝４である）を含む粒子が生成すると考えられる（なお、このような粒子もセリウム水酸化物である）。Ｃｅ（ＯＨ）ａＸｂでは、電子吸引性の陰イオン（Ｘｃ－）が作用して水酸化物イオンの反応性が向上しており、Ｃｅ（ＯＨ）ａＸｂの存在量が増加するに伴い研磨速度が向上すると考えられる。陰イオン（Ｘｃ－）としては、例えば、ＮＯ３ －及びＳＯ４ ２－が挙げられる。セリウム水酸化物を含む粒子は、Ｃｅ（ＯＨ）ａＸｂだけでなく、Ｃｅ（ＯＨ）４、ＣｅＯ２等も含み得ると考えられる。 Ce (OH) a X b composed of cerium ion, one to three hydroxide ions (OH − ) and one to three anions (X c− ), depending on the production conditions of the cerium hydroxide and the like. It is believed that particles containing (where a + b × c = 4) are produced (note that such particles are also cerium hydroxide). In Ce (OH) a X b , the reactivity of hydroxide ions is improved by the action of an electron-withdrawing anion (X c− ), and the abundance of Ce (OH) a X b increases. It is thought that the polishing rate increases with the increase in the polishing rate. Examples of the anion (X c− ) include NO 3 — and SO 4 2- . It is thought that the particles containing cerium hydroxide may include not only Ce (OH) a Xb but also Ce (OH) 4 , CeO 2 and the like.
　セリウム水酸化物を含む粒子がＣｅ（ＯＨ）ａＸｂを含むことは、粒子を純水でよく洗浄した後に、ＦＴ－ＩＲ　ＡＴＲ法（Ｆｏｕｒｉｅｒ　ｔｒａｎｓｆｏｒｍ　Ｉｎｆｒａ　Ｒｅｄ　Ｓｐｅｃｔｒｏｍｅｔｅｒ　Ａｔｔｅｎｕａｔｅｄ　Ｔｏｔａｌ　Ｒｅｆｌｅｃｔｉｏｎ法、フーリエ変換赤外分光光度計全反射測定法）で、陰イオン（Ｘｃ－）に該当するピークを検出する方法により確認できる。Ｘ線光電子分光法により、陰イオン（Ｘｃ－）の存在を確認することもできる。 The fact that the particles containing cerium hydroxide contain Ce (OH) a Xb is based on the fact that the particles are thoroughly washed with pure water and then the FT-IR ATR method (Fourier transform Infra Red Spectrometer Attenuated Total Reflection method, Fourier transform method) It can be confirmed by a method of detecting a peak corresponding to an anion (X c− ) by a spectrophotometer total reflection measurement method). X-ray photoelectron spectroscopy can also confirm the presence of an anion (X c− ).
　スラリ中の砥粒の平均粒径（平均二次粒径）は、下記の範囲が好ましい。砥粒の平均粒径の下限は、絶縁材料の研磨速度が更に向上する観点から、１６ｎｍ以上が好ましく、２０ｎｍ以上がより好ましく、３０ｎｍ以上が更に好ましく、４０ｎｍ以上が特に好ましく、５０ｎｍ以上が極めて好ましく、１００ｎｍ以上が非常に好ましく、１２０ｎｍ以上がより一層好ましく、１４０ｎｍ以上が更に好ましい。砥粒の平均粒径の上限は、砥粒の分散性が向上する観点、及び、被研磨面に傷がつくことが抑制されやすい観点から、１０５０ｎｍ以下が好ましく、１０００ｎｍ以下がより好ましく、８００ｎｍ以下が更に好ましく、６００ｎｍ以下が特に好ましく、５００ｎｍ以下が極めて好ましく、４００ｎｍ以下が非常に好ましく、３００ｎｍ以下がより一層好ましく、２００ｎｍ以下が更に好ましく、１６０ｎｍ以下が特に好ましく、１５５ｎｍ以下が極めて好ましい。前記観点から、砥粒の平均粒径は、１６～１０５０ｎｍであることがより好ましい。 平均 The average particle size (average secondary particle size) of the abrasive grains in the slurry is preferably in the following range. The lower limit of the average particle size of the abrasive grains is preferably 16 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, particularly preferably 40 nm or more, and most preferably 50 nm or more, from the viewpoint of further improving the polishing rate of the insulating material. , 100 nm or more is very preferable, 120 nm or more is more preferable, and 140 nm or more is further preferable. The upper limit of the average particle size of the abrasive grains is preferably 1050 nm or less, more preferably 1000 nm or less, and 800 nm or less, from the viewpoint of improving the dispersibility of the abrasive grains and from the viewpoint that the surface to be polished is easily suppressed from being damaged. Is more preferably, particularly preferably 600 nm or less, particularly preferably 500 nm or less, very preferably 400 nm or less, still more preferably 300 nm or less, further preferably 200 nm or less, particularly preferably 160 nm or less, and most preferably 155 nm or less. From the above viewpoint, the average particle diameter of the abrasive grains is more preferably 16 to 1050 nm.
　平均粒径は、例えば、光回折散乱式粒度分布計（例えば、ベックマン・コールター株式会社製、商品名：Ｎ５、又は、マイクロトラック・ベル株式会社製、商品名：マイクロトラックＭＴ３３００ＥＸＩＩ）を用いて測定することができる。 The average particle size is measured using, for example, a light diffraction scattering type particle size distribution meter (for example, trade name: N5, manufactured by Beckman Coulter, Inc., or Microtrac Bell, Inc., trade name: Microtrac MT3300EXII). can do.
　スラリ中における砥粒のゼータ電位（砥粒全体のゼータ電位）は、下記の範囲が好ましい。砥粒のゼータ電位は、絶縁材料の研磨速度が更に向上する観点から、＋１０ｍＶ以上が好ましく、＋２０ｍＶ以上がより好ましく、＋２５ｍＶ以上が更に好ましく、＋３０ｍＶ以上が特に好ましく、＋４０ｍＶ以上が極めて好ましく、＋５０ｍＶ以上が非常に好ましい。砥粒のゼータ電位の上限は、特に限定されず、例えば＋２００ｍＶ以下である。 The zeta potential of the abrasive grains in the slurry (the zeta potential of the entire abrasive grains) is preferably in the following range. The zeta potential of the abrasive grains is preferably at least +10 mV, more preferably at least +20 mV, still more preferably at least +25 mV, particularly preferably at least +30 mV, particularly preferably at least +40 mV, particularly preferably at least +40 mV, from the viewpoint of further improving the polishing rate of the insulating material. Is highly preferred. The upper limit of the zeta potential of the abrasive grains is not particularly limited, and is, for example, +200 mV or less.
　ゼータ電位とは、粒子の表面電位を表す。ゼータ電位は、例えば、動的光散乱式ゼータ電位測定装置（例えば、ベックマン・コールター株式会社製、商品名：ＤｅｌｓａＮａｎｏ　Ｃ）を用いて測定することができる。粒子のゼータ電位は、添加剤を用いて調整できる。例えば、セリウム酸化物を含有する粒子にモノカルボン酸（例えば酢酸）を接触させることにより、正のゼータ電位を有する粒子を得ることができる。また、セリウム酸化物を含有する粒子に、リン酸二水素アンモニウム、カルボキシル基を有する材料（例えばポリアクリル酸）等を接触させることにより、負のゼータ電位を有する粒子を得ることができる。 The zeta potential indicates the surface potential of the particles. The zeta potential can be measured using, for example, a dynamic light scattering zeta potential measuring device (for example, trade name: DelsaNano @ C, manufactured by Beckman Coulter, Inc.). The zeta potential of the particles can be adjusted using additives. For example, by bringing a monocarboxylic acid (for example, acetic acid) into contact with particles containing cerium oxide, particles having a positive zeta potential can be obtained. Further, particles having a negative zeta potential can be obtained by bringing ammonium dihydrogen phosphate, a material having a carboxyl group (eg, polyacrylic acid) or the like into contact with particles containing cerium oxide.
　砥粒におけるセリウム酸化物の含有量の下限は、絶縁材料の研磨速度が更に向上する観点から、砥粒全体（スラリに含まれる砥粒全体）を基準として、５０質量％以上が好ましく、５０質量％を超えることがより好ましく、６０質量％以上が更に好ましく、７０質量％以上が特に好ましく、７５質量％以上が極めて好ましく、８０質量％以上が非常に好ましく、８５質量％以上がより一層好ましく、９０質量％以上が更に好ましい。砥粒におけるセリウム酸化物の含有量の上限は、砥粒全体を基準として１００質量％であってよい。前記観点から、砥粒におけるセリウム酸化物の含有量は、砥粒全体を基準として５０～１００質量％であってよい。 The lower limit of the cerium oxide content in the abrasive grains is preferably 50% by mass or more, and more preferably 50% by mass, based on the entire abrasive grains (the entire abrasive grains contained in the slurry) from the viewpoint of further improving the polishing rate of the insulating material. %, More preferably 60% by mass or more, particularly preferably 70% by mass or more, particularly preferably 75% by mass or more, very preferably 80% by mass or more, even more preferably 85% by mass or more. 90 mass% or more is more preferable. The upper limit of the cerium oxide content in the abrasive grains may be 100% by mass based on the entire abrasive grains. From the above viewpoint, the content of the cerium oxide in the abrasive grains may be 50 to 100% by mass based on the entire abrasive grains.
　砥粒におけるセリウム水酸化物の含有量の下限は、絶縁材料の研磨速度が更に向上する観点から、砥粒全体（スラリに含まれる砥粒全体）を基準として、５質量％以上が好ましく、７質量％以上がより好ましく、９質量％以上が更に好ましい。砥粒におけるセリウム水酸化物の含有量の上限は、砥粒全体を基準として１００質量％であってよい。前記観点から、砥粒におけるセリウム水酸化物の含有量は、砥粒全体を基準として９～１００質量％であってよい。砥粒がセリウム酸化物及びセリウム水酸化物を含有する場合、砥粒におけるセリウム水酸化物の含有量の上限は、砥粒全体を基準として、５０質量％以下が好ましく、５０質量％未満がより好ましく、４０質量％以下が更に好ましく、３０質量％以下が特に好ましく、２０質量％以下が極めて好ましく、１０質量％以下が非常に好ましい。 The lower limit of the content of cerium hydroxide in the abrasive grains is preferably 5% by mass or more based on the entire abrasive grains (the entire abrasive grains contained in the slurry) from the viewpoint of further improving the polishing rate of the insulating material. It is more preferably at least 9 mass%, further preferably at least 9 mass%. The upper limit of the cerium hydroxide content in the abrasive grains may be 100% by mass based on the entire abrasive grains. From the above viewpoint, the content of cerium hydroxide in the abrasive grains may be 9 to 100% by mass based on the entire abrasive grains. When the abrasive contains cerium oxide and cerium hydroxide, the upper limit of the content of cerium hydroxide in the abrasive is preferably 50% by mass or less, more preferably less than 50% by mass, based on the entire abrasive. Preferably, it is more preferably 40% by mass or less, particularly preferably 30% by mass or less, particularly preferably 20% by mass or less, and very preferably 10% by mass or less.
　スラリにおけるセリウム酸化物の含有量の下限は、絶縁材料の研磨速度が更に向上する観点から、スラリの全質量を基準として、０．００５質量％以上が好ましく、０．００８質量％以上がより好ましく、０．０１質量％以上が更に好ましく、０．０５質量％以上が特に好ましく、０．０８質量％以上が極めて好ましく、０．１質量％以上が非常に好ましく、０．１５質量％以上がより一層好ましく、０．１８質量％以上が更に好ましい。スラリにおけるセリウム酸化物の含有量の上限は、スラリの保存安定性を高くする観点から、スラリの全質量を基準として、５質量％以下が好ましく、３質量％以下がより好ましく、１質量％以下が更に好ましく、０．５質量％以下が特に好ましく、０．３質量％以下が極めて好ましく、０．２質量％以下が非常に好ましい。前記観点から、スラリにおけるセリウム酸化物の含有量は、スラリの全質量を基準として０．００５～５質量％であることがより好ましい。 The lower limit of the content of cerium oxide in the slurry is preferably 0.005% by mass or more, more preferably 0.008% by mass or more based on the total mass of the slurry, from the viewpoint of further improving the polishing rate of the insulating material. , 0.01% by mass or more is further preferable, 0.05% by mass or more is particularly preferable, 0.08% by mass or more is very preferable, 0.1% by mass or more is very preferable, and 0.15% by mass or more is more preferable. More preferably, it is more preferably 0.18% by mass or more. The upper limit of the content of cerium oxide in the slurry is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass or less, based on the total mass of the slurry, from the viewpoint of increasing the storage stability of the slurry. Is more preferably 0.5% by mass or less, particularly preferably 0.3% by mass or less, and very preferably 0.2% by mass or less. From the above viewpoint, the content of cerium oxide in the slurry is more preferably 0.005 to 5% by mass based on the total mass of the slurry.
　スラリにおけるセリウム水酸化物の含有量の下限は、砥粒と被研磨面との化学的な相互作用が更に向上して絶縁材料の研磨速度が更に向上する観点から、スラリの全質量を基準として、０．００５質量％以上が好ましく、０．００８質量％以上がより好ましく、０．０１質量％以上が更に好ましく、０．０１２質量％以上が特に好ましく、０．０１５質量％以上が極めて好ましく、０．０１８質量％以上が非常に好ましい。スラリにおけるセリウム水酸化物の含有量の上限は、砥粒の凝集を避けることが容易になると共に、砥粒と被研磨面との化学的な相互作用が更に良好となり、砥粒の特性を有効に活用しやすい観点から、スラリの全質量を基準として、５質量％以下が好ましく、３質量％以下がより好ましく、１質量％以下が更に好ましく、０．５質量％以下が特に好ましく、０．２質量％以下が極めて好ましい。前記観点から、スラリにおけるセリウム水酸化物の含有量は、スラリの全質量を基準として、０．００５～５質量％であることがより好ましい。砥粒がセリウム酸化物及びセリウム水酸化物を含有する場合、スラリにおけるセリウム水酸化物の含有量の上限は、スラリの全質量を基準として、０．１質量％以下が好ましく、０．０５質量％以下がより好ましく、０．０３質量％以下が更に好ましく、０．０２質量％以下が特に好ましい。 The lower limit of the content of cerium hydroxide in the slurry is based on the total mass of the slurry, from the viewpoint that the chemical interaction between the abrasive grains and the surface to be polished is further improved and the polishing rate of the insulating material is further improved. , 0.005% by mass or more, more preferably 0.008% by mass or more, still more preferably 0.01% by mass or more, particularly preferably 0.012% by mass or more, and very preferably 0.015% by mass or more, Higher than 0.018% by weight is very preferred. The upper limit of the content of cerium hydroxide in the slurry makes it easier to avoid agglomeration of the abrasive grains, and further enhances the chemical interaction between the abrasive grains and the surface to be polished, thereby improving the properties of the abrasive grains. From the viewpoint of easy utilization, the amount is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, based on the total mass of the slurry. It is very preferably at most 2% by mass. From the above viewpoint, the content of the cerium hydroxide in the slurry is more preferably 0.005 to 5% by mass based on the total mass of the slurry. When the abrasive contains cerium oxide and cerium hydroxide, the upper limit of the content of cerium hydroxide in the slurry is preferably 0.1% by mass or less, based on the total mass of the slurry, and 0.05% by mass. % Or less, more preferably 0.03% by mass or less, and particularly preferably 0.02% by mass or less.
　スラリにおける砥粒の含有量の下限は、絶縁材料の研磨速度が更に向上する観点から、スラリの全質量を基準として、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上が更に好ましく、０．１２質量％以上が特に好ましく、０．１４質量％以上が極めて好ましく、０．１６質量％以上が非常に好ましく、０．１８質量％以上がより一層好ましく、０．２質量％以上が更に好ましい。スラリにおける砥粒の含有量の上限は、スラリの保存安定性を高くする観点から、スラリの全質量を基準として、１０質量％以下が好ましく、５質量％以下がより好ましく、１質量％以下が更に好ましく、０．５質量％以下が特に好ましく、０．３質量％以下が極めて好ましい。前記観点から、スラリにおける砥粒の含有量は、スラリの全質量を基準として０．０１～１０質量％であることがより好ましい。 The lower limit of the content of the abrasive grains in the slurry is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total mass of the slurry, from the viewpoint of further improving the polishing rate of the insulating material. 0.1 mass% or more is still more preferable, 0.12 mass% or more is especially preferable, 0.14 mass% or more is very preferable, 0.16 mass% or more is very preferable, and 0.18 mass% or more is much more preferable. It is preferably at least 0.2% by mass. The upper limit of the content of the abrasive grains in the slurry is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 1% by mass or less, based on the total mass of the slurry, from the viewpoint of increasing the storage stability of the slurry. The content is more preferably 0.5% by mass or less, particularly preferably 0.3% by mass or less. From the above viewpoint, the content of the abrasive grains in the slurry is more preferably 0.01 to 10% by mass based on the total mass of the slurry.
　砥粒は、金属Ｍを含む金属化合物を含む粒子を含有していればよく、金属Ｍを含まない粒子を含有してもよい。砥粒は、互いに接触した複数の粒子から構成される複合粒子を含んでいてよい。例えば、砥粒は、第１の粒子と、当該第１の粒子に接触した第２の粒子と、を含む複合粒子を含んでいてよく、複合粒子と遊離粒子（例えば、第１の粒子と接触していない第２の粒子）とを含んでいてよい。 Abrasive particles may contain particles containing a metal compound containing metal M, and may contain particles containing no metal M. The abrasive grains may include composite particles composed of a plurality of particles in contact with each other. For example, the abrasive grains may include composite particles comprising a first particle and a second particle in contact with the first particle, wherein the composite particle and free particles (eg, contact with the first particle) Second particles).
　本実施形態に係るスラリの砥粒は、絶縁材料の研磨速度が更に向上する観点から、第１の粒子と、当該第１の粒子に接触した第２の粒子と、を含み、第２の粒子の粒径が第１の粒子の粒径よりも小さく、第１の粒子がセリウム酸化物を含有し、第２の粒子がセリウム化合物を含有する態様であることが好ましい。このような砥粒を用いることにより絶縁材料（例えば酸化珪素）の研磨速度を更に向上させることができる。このように絶縁材料の研磨速度が向上する理由としては、例えば、下記の理由が挙げられる。但し、理由は下記に限定されない。 The abrasive grains of the slurry according to the present embodiment include first particles and second particles in contact with the first particles, from the viewpoint of further improving the polishing rate of the insulating material, and include second particles. Is smaller than the particle size of the first particles, the first particles contain cerium oxide, and the second particles contain a cerium compound. By using such abrasive grains, the polishing rate of an insulating material (for example, silicon oxide) can be further improved. The reasons why the polishing rate of the insulating material is improved as described above include, for example, the following reasons. However, the reason is not limited to the following.
　すなわち、セリウム酸化物を含有すると共に、第２の粒子よりも大きい粒径を有する第１の粒子は、第２の粒子と比較して、絶縁材料に対する機械的作用（メカニカル性）が強い。一方、セリウム化合物を含有すると共に、第１の粒子よりも小さい粒径を有する第２の粒子は、第１の粒子と比較して、絶縁材料に対する機械的作用は小さいものの、粒子全体における比表面積（単位質量当たりの表面積）が大きいため、絶縁材料に対する化学的作用（ケミカル性）が強い。このように、機械的作用が強い第１の粒子と、化学的作用が強い第２の粒子と、を併用することにより研磨速度向上の相乗効果が得られやすい。 That is, the first particles containing cerium oxide and having a larger particle size than the second particles have stronger mechanical action (mechanical properties) on the insulating material than the second particles. On the other hand, the second particles containing the cerium compound and having a smaller particle size than the first particles have a smaller mechanical action on the insulating material than the first particles, but have a specific surface area of the whole particles. Since the surface area per unit mass is large, the chemical action (chemical properties) on the insulating material is strong. As described above, by using the first particles having a strong mechanical action and the second particles having a strong chemical action together, a synergistic effect of improving the polishing rate is easily obtained.
　第２の粒子のセリウム化合物としては、セリウム水酸化物、セリウム酸化物等が挙げられる。第２の粒子のセリウム化合物としては、セリウム酸化物とは異なる化合物を用いることができる。セリウム化合物は、絶縁材料の研磨速度が更に向上する観点から、セリウム水酸化物を含むことが好ましい。 セ Examples of the cerium compound of the second particles include cerium hydroxide and cerium oxide. As the cerium compound of the second particles, a compound different from cerium oxide can be used. The cerium compound preferably contains cerium hydroxide from the viewpoint of further improving the polishing rate of the insulating material.
　第２の粒子の粒径は、第１の粒子の粒径よりも小さいことが好ましい。第１の粒子及び第２の粒子の粒径の大小関係は、複合粒子のＳＥＭ画像等から判別することができる。一般的に、粒径が小さい粒子では、粒径が大きい粒子に比べて単位質量当たりの表面積が大きいことから反応活性が高い。一方、粒径が小さい粒子の機械的作用（機械的研磨力）は、粒径が大きい粒子に比べて小さい。しかしながら、本実施形態においては、第２の粒子の粒径が第１の粒子の粒径より小さい場合であっても、第１の粒子及び第２の粒子の相乗効果を発現させることが可能であり、優れた反応活性及び機械的作用を容易に両立することができる。 粒径 The particle size of the second particles is preferably smaller than the particle size of the first particles. The magnitude relationship between the particle diameters of the first particles and the second particles can be determined from an SEM image or the like of the composite particles. Generally, particles having a small particle diameter have a higher surface activity per unit mass than particles having a large particle diameter, and thus have high reaction activity. On the other hand, the mechanical action (mechanical polishing force) of particles having a small particle size is smaller than that of particles having a large particle size. However, in the present embodiment, even when the particle size of the second particles is smaller than the particle size of the first particles, it is possible to exhibit a synergistic effect between the first particles and the second particles. It is possible to easily achieve both excellent reaction activity and mechanical action.
　第１の粒子の粒径の下限は、絶縁材料の研磨速度が更に向上する観点から、１５ｎｍ以上が好ましく、２５ｎｍ以上がより好ましく、３５ｎｍ以上が更に好ましく、４０ｎｍ以上が特に好ましく、５０ｎｍ以上が極めて好ましく、８０ｎｍ以上が非常に好ましく、１００ｎｍ以上がより一層好ましい。第１の粒子の粒径の上限は、砥粒の分散性が向上する観点、及び、被研磨面に傷がつくことが抑制されやすい観点から、１０００ｎｍ以下が好ましく、８００ｎｍ以下がより好ましく、６００ｎｍ以下が更に好ましく、４００ｎｍ以下が特に好ましく、３００ｎｍ以下が極めて好ましく、２００ｎｍ以下が非常に好ましく、１５０ｎｍ以下がより一層好ましい。前記観点から、第１の粒子の粒径は、１５～１０００ｎｍであることがより好ましい。第１の粒子の平均粒径（平均二次粒径）が上述の範囲であってもよい。 The lower limit of the particle diameter of the first particles is preferably 15 nm or more, more preferably 25 nm or more, still more preferably 35 nm or more, particularly preferably 40 nm or more, and most preferably 50 nm or more, from the viewpoint of further improving the polishing rate of the insulating material. Preferably, 80 nm or more is very preferable, and 100 nm or more is still more preferable. The upper limit of the particle diameter of the first particles is preferably 1,000 nm or less, more preferably 800 nm or less, and 600 nm or less, from the viewpoint of improving the dispersibility of the abrasive grains, and from the viewpoint that scratches on the surface to be polished are easily suppressed. The following is still more preferred, particularly preferably 400 nm or less, particularly preferably 300 nm or less, very preferably 200 nm or less, and even more preferably 150 nm or less. From the above viewpoint, the particle diameter of the first particles is more preferably 15 to 1000 nm. The average particle size (average secondary particle size) of the first particles may be in the above range.
　第２の粒子の粒径の下限は、絶縁材料の研磨速度が更に向上する観点から、１ｎｍ以上が好ましく、２ｎｍ以上がより好ましく、３ｎｍ以上が更に好ましい。第２の粒子の粒径の上限は、砥粒の分散性が向上する観点、及び、被研磨面に傷がつくことが抑制されやすい観点から、５０ｎｍ以下が好ましく、３０ｎｍ以下がより好ましく、２５ｎｍ以下が更に好ましく、２０ｎｍ以下が特に好ましく、１５ｎｍ以下が極めて好ましく、１０ｎｍ以下が非常に好ましい。前記観点から、第２の粒子の粒径は、１～５０ｎｍであることがより好ましい。第２の粒子の平均粒径（平均二次粒径）が上述の範囲であってもよい。 下限 The lower limit of the particle size of the second particles is preferably 1 nm or more, more preferably 2 nm or more, and still more preferably 3 nm or more, from the viewpoint of further improving the polishing rate of the insulating material. The upper limit of the particle size of the second particles is preferably 50 nm or less, more preferably 30 nm or less, and 25 nm from the viewpoint that the dispersibility of the abrasive grains is improved and that the surface to be polished is easily suppressed from being damaged. The following is more preferred, the thickness is particularly preferably 20 nm or less, particularly preferably 15 nm or less, and very preferably 10 nm or less. From the above viewpoint, the particle size of the second particles is more preferably 1 to 50 nm. The average particle size (average secondary particle size) of the second particles may be in the above range.
　第１の粒子は、負のゼータ電位を有することができる。第２の粒子は、正のゼータ電位を有することができる。 １ The first particles can have a negative zeta potential. The second particles can have a positive zeta potential.
　第１の粒子及び第２の粒子を含む複合粒子は、ホモジナイザー、ナノマイザー、ボールミル、ビーズミル、超音波処理機等を用いて第１の粒子と第２の粒子とを接触させること、互いに相反する電荷を有する第１の粒子と第２の粒子とを接触させること、粒子の含有量が少ない状態で第１の粒子と第２の粒子とを接触させることなどにより得ることができる。 The composite particles including the first particles and the second particles are brought into contact with the first particles and the second particles using a homogenizer, a nanomizer, a ball mill, a bead mill, an ultrasonic treatment machine, or the like, and the charges opposite to each other are used. Can be obtained by contacting the first particles with the second particles having the following, or by bringing the first particles and the second particles into contact with each other with a small content of the particles.
　第１の粒子におけるセリウム酸化物の含有量の下限は、絶縁材料の研磨速度が更に向上する観点から、第１の粒子の全体（スラリに含まれる第１の粒子の全体。以下同様）を基準として、５０質量％以上が好ましく、７０質量％以上がより好ましく、９０質量％以上が更に好ましく、９５質量％以上が特に好ましい。第１の粒子は、実質的にセリウム酸化物からなる態様（実質的に第１の粒子の１００質量％がセリウム酸化物である態様）であってもよい。 The lower limit of the content of cerium oxide in the first particles is based on the entire first particles (the entire first particles contained in the slurry; the same applies hereinafter) from the viewpoint of further improving the polishing rate of the insulating material. Is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The first particles may be in an aspect substantially composed of cerium oxide (an aspect in which 100% by mass of the first particles is cerium oxide).
　第２の粒子におけるセリウム化合物の含有量の下限は、絶縁材料の研磨速度が更に向上する観点から、第２の粒子の全体（スラリに含まれる第２の粒子の全体。以下同様）を基準として、５０質量％以上が好ましく、７０質量％以上がより好ましく、９０質量％以上が更に好ましく、９５質量％以上が特に好ましい。第２の粒子は、実質的にセリウム化合物からなる態様（実質的に第２の粒子の１００質量％がセリウム化合物である態様）であってもよい。 The lower limit of the content of the cerium compound in the second particles is based on the entire second particles (the entire second particles contained in the slurry; the same applies hereinafter) from the viewpoint of further improving the polishing rate of the insulating material. , 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The second particles may have an aspect substantially composed of a cerium compound (an aspect in which substantially 100% by mass of the second particles is a cerium compound).
　スラリに特定の波長の光を透過させた際に分光光度計によって得られる下記式の吸光度の値により第２の粒子の含有量を推定することができる。すなわち、粒子が特定の波長の光を吸収する場合、当該粒子を含む領域の光透過率が減少する。光透過率は、粒子による吸収だけでなく、散乱によっても減少するが、第２の粒子では、散乱の影響が小さい。そのため、本実施形態では、下記式によって算出される吸光度の値により第２の粒子の含有量を推定することができる。
　吸光度　＝－ＬＯＧ１０（光透過率［％］／１００） The content of the second particles can be estimated from the absorbance value of the following equation obtained by a spectrophotometer when light having a specific wavelength is transmitted through the slurry. That is, when the particles absorb light of a specific wavelength, the light transmittance of the region including the particles decreases. Although the light transmittance decreases not only due to absorption by the particles but also due to scattering, the effect of the scattering is small for the second particles. Therefore, in the present embodiment, the content of the second particles can be estimated from the absorbance value calculated by the following equation.
Absorbance = -LOG 10 (Light transmittance [%] / 100)
　砥粒における第１の粒子の含有量の下限は、絶縁材料の研磨速度が更に向上する観点から、砥粒全体（スラリに含まれる砥粒全体。以下同様）を基準として、５０質量％以上が好ましく、５０質量％を超えることがより好ましく、６０質量％以上が更に好ましく、７０質量％以上が特に好ましく、７５質量％以上が極めて好ましく、８０質量％以上が非常に好ましく、８５質量％以上がより一層好ましく、９０質量％以上が更に好ましい。砥粒における第１の粒子の含有量の上限は、絶縁材料の研磨速度が更に向上する観点から、砥粒全体を基準として、９５質量％以下が好ましく、９３質量％以下がより好ましく、９１質量％以下が更に好ましい。前記観点から、砥粒における第１の粒子の含有量は、砥粒全体を基準として５０～９５質量％であることがより好ましい。 From the viewpoint of further improving the polishing rate of the insulating material, the lower limit of the content of the first particles in the abrasive grains is 50% by mass or more based on the entire abrasive grains (the entirety of the abrasive grains contained in the slurry. The same applies hereinafter). Preferably, it is more preferably more than 50% by mass, still more preferably 60% by mass or more, particularly preferably 70% by mass or more, very preferably 75% by mass or more, very preferably 80% by mass or more, and 85% by mass or more. Even more preferred is 90% by mass or more. The upper limit of the content of the first particles in the abrasive grains is preferably 95% by mass or less, more preferably 93% by mass or less, and more preferably 91% by mass, based on the entire abrasive particles, from the viewpoint of further improving the polishing rate of the insulating material. % Is more preferable. From the above viewpoint, the content of the first particles in the abrasive grains is more preferably 50 to 95% by mass based on the entire abrasive grains.
　砥粒における第２の粒子の含有量の下限は、絶縁材料の研磨速度が更に向上する観点から、砥粒全体（スラリに含まれる砥粒全体）を基準として、５質量％以上が好ましく、７質量％以上がより好ましく、９質量％以上が更に好ましい。砥粒における第２の粒子の含有量の上限は、絶縁材料の研磨速度が更に向上する観点から、砥粒全体を基準として、５０質量％以下が好ましく、５０質量％未満がより好ましく、４０質量％以下が更に好ましく、３０質量％以下が特に好ましく、２０質量％以下が極めて好ましく、１０質量％以下が非常に好ましい。前記観点から、砥粒における第２の粒子の含有量は、砥粒全体を基準として５～５０質量％であることがより好ましい。 From the viewpoint of further improving the polishing rate of the insulating material, the lower limit of the content of the second particles in the abrasive grains is preferably 5% by mass or more based on the entire abrasive grains (the entire abrasive grains contained in the slurry). It is more preferably at least 9 mass%, further preferably at least 9 mass%. The upper limit of the content of the second particles in the abrasive grains is preferably 50% by mass or less, more preferably less than 50% by mass, and more preferably 40% by mass, based on the entire abrasive particles, from the viewpoint of further improving the polishing rate of the insulating material. %, More preferably 30% by mass or less, particularly preferably 20% by mass or less, and very preferably 10% by mass or less. From the above viewpoint, the content of the second particles in the abrasive grains is more preferably 5 to 50% by mass based on the entire abrasive grains.
　第１の粒子の含有量の下限は、絶縁材料の研磨速度が更に向上する観点から、第１の粒子及び第２の粒子の合計量を基準として、５０質量％以上が好ましく、５０質量％を超えることがより好ましく、６０質量％以上が更に好ましく、７０質量％以上が特に好ましく、７５質量％以上が極めて好ましく、８０質量％以上が非常に好ましく、８５質量％以上がより一層好ましく、９０質量％以上が更に好ましい。第１の粒子の含有量の上限は、絶縁材料の研磨速度が更に向上する観点から、第１の粒子及び第２の粒子の合計量を基準として、９５質量％以下が好ましく、９３質量％以下がより好ましく、９１質量％以下が更に好ましい。前記観点から、第１の粒子の含有量は、第１の粒子及び第２の粒子の合計量を基準として５０～９５質量％であることがより好ましい。 The lower limit of the content of the first particles is preferably 50% by mass or more, and more preferably 50% by mass, based on the total amount of the first particles and the second particles, from the viewpoint of further improving the polishing rate of the insulating material. More preferably, it is more preferably 60% by mass or more, particularly preferably 70% by mass or more, particularly preferably 75% by mass or more, very preferably 80% by mass or more, still more preferably 85% by mass or more, and 90% by mass. % Or more is more preferable. From the viewpoint of further improving the polishing rate of the insulating material, the upper limit of the content of the first particles is preferably 95% by mass or less, and more preferably 93% by mass or less, based on the total amount of the first particles and the second particles. Is more preferable, and 91 mass% or less is still more preferable. From the above viewpoint, the content of the first particles is more preferably 50 to 95% by mass based on the total amount of the first particles and the second particles.
　第２の粒子の含有量の下限は、絶縁材料の研磨速度が更に向上する観点から、第１の粒子及び第２の粒子の合計量を基準として、５質量％以上が好ましく、７質量％以上がより好ましく、９質量％以上が更に好ましい。第２の粒子の含有量の上限は、絶縁材料の研磨速度が更に向上する観点から、第１の粒子及び第２の粒子の合計量を基準として、５０質量％以下が好ましく、５０質量％未満がより好ましく、４０質量％以下が更に好ましく、３０質量％以下が特に好ましく、２０質量％以下が極めて好ましく、１０質量％以下が非常に好ましい。前記観点から、第２の粒子の含有量は、第１の粒子及び第２の粒子の合計量を基準として５～５０質量％であることがより好ましい。 The lower limit of the content of the second particles is preferably 5% by mass or more, more preferably 7% by mass or more based on the total amount of the first particles and the second particles, from the viewpoint of further improving the polishing rate of the insulating material. Is more preferable, and 9 mass% or more is further preferable. The upper limit of the content of the second particles is preferably 50% by mass or less, and less than 50% by mass, based on the total amount of the first particles and the second particles, from the viewpoint of further improving the polishing rate of the insulating material. Is more preferably 40% by mass or less, further preferably 30% by mass or less, particularly preferably 20% by mass or less, and very preferably 10% by mass or less. From the above viewpoint, the content of the second particles is more preferably 5 to 50% by mass based on the total amount of the first particles and the second particles.
　スラリにおける第１の粒子の含有量の下限は、絶縁材料の研磨速度が更に向上する観点から、スラリの全質量を基準として、０．００５質量％以上が好ましく、０．００８質量％以上がより好ましく、０．０１質量％以上が更に好ましく、０．０５質量％以上が特に好ましく、０．０８質量％以上が極めて好ましく、０．１質量％以上が非常に好ましく、０．１５質量％以上がより一層好ましく、０．１８質量％以上が更に好ましい。スラリにおける第１の粒子の含有量の上限は、スラリの保存安定性を高くする観点から、スラリの全質量を基準として、５質量％以下が好ましく、３質量％以下がより好ましく、１質量％以下が更に好ましく、０．５質量％以下が特に好ましく、０．３質量％以下が極めて好ましく、０．２質量％以下が非常に好ましい。前記観点から、スラリにおける第１の粒子の含有量は、スラリの全質量を基準として０．００５～５質量％であることがより好ましい。 The lower limit of the content of the first particles in the slurry is preferably 0.005% by mass or more, more preferably 0.008% by mass or more based on the total mass of the slurry, from the viewpoint of further improving the polishing rate of the insulating material. It is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, particularly preferably at least 0.08% by mass, very preferably at least 0.1% by mass, and at least 0.15% by mass. It is even more preferably 0.18% by mass or more. From the viewpoint of increasing the storage stability of the slurry, the upper limit of the content of the first particles in the slurry is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass, based on the total mass of the slurry. The content is more preferably 0.5% by mass or less, particularly preferably 0.3% by mass or less, and very preferably 0.2% by mass or less. From the above viewpoint, the content of the first particles in the slurry is more preferably 0.005 to 5% by mass based on the total mass of the slurry.
　スラリにおける第２の粒子の含有量の下限は、砥粒と被研磨面との化学的な相互作用が更に向上して絶縁材料の研磨速度が更に向上する観点から、スラリの全質量を基準として、０．００５質量％以上が好ましく、０．００８質量％以上がより好ましく、０．０１質量％以上が更に好ましく、０．０１２質量％以上が特に好ましく、０．０１５質量％以上が極めて好ましく、０．０１８質量％以上が非常に好ましい。スラリにおける第２の粒子の含有量の上限は、砥粒の凝集を避けることが容易になると共に、砥粒と被研磨面との化学的な相互作用が更に良好となり、砥粒の特性を有効に活用しやすい観点から、スラリの全質量を基準として、５質量％以下が好ましく、３質量％以下がより好ましく、１質量％以下が更に好ましく、０．５質量％以下が特に好ましく、０．２質量％以下が極めて好ましく、０．１質量％以下が非常に好ましく、０．０５質量％以下がより一層好ましく、０．０３質量％以下が更に好ましく、０．０２質量％以下が特に好ましい。前記観点から、スラリにおける第２の粒子の含有量は、スラリの全質量を基準として０．００５～５質量％であることがより好ましい。 The lower limit of the content of the second particles in the slurry is based on the total mass of the slurry, from the viewpoint that the chemical interaction between the abrasive grains and the surface to be polished is further improved and the polishing rate of the insulating material is further improved. , 0.005% by mass or more, more preferably 0.008% by mass or more, still more preferably 0.01% by mass or more, particularly preferably 0.012% by mass or more, and very preferably 0.015% by mass or more, Higher than 0.018% by weight is very preferred. The upper limit of the content of the second particles in the slurry makes it easier to avoid agglomeration of the abrasive grains, further enhances the chemical interaction between the abrasive grains and the surface to be polished, and improves the properties of the abrasive grains. From the viewpoint of easy utilization, the amount is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, based on the total mass of the slurry. It is very preferably at most 2% by mass, particularly preferably at most 0.1% by mass, further preferably at most 0.05% by mass, further preferably at most 0.03% by mass, particularly preferably at most 0.02% by mass. From the above viewpoint, the content of the second particles in the slurry is more preferably 0.005 to 5% by mass based on the total mass of the slurry.
（液状媒体）
　液状媒体としては、特に制限はないが、脱イオン水、超純水等の水が好ましい。液状媒体の含有量は、他の構成成分の含有量を除いたスラリの残部でよく、特に限定されない。 (Liquid medium)
The liquid medium is not particularly limited, but water such as deionized water and ultrapure water is preferable. The content of the liquid medium may be the remainder of the slurry excluding the content of other components, and is not particularly limited.
（任意成分）
　本実施形態に係るスラリは、任意の添加剤を更に含有していてもよい。任意の添加剤としては、カルボキシル基を有する材料（ポリオキシアルキレン化合物又は水溶性高分子に該当する化合物を除く）、ポリオキシアルキレン化合物、水溶性高分子、酸化剤（例えば過酸化水素）、分散剤（例えばリン酸系無機塩）等が挙げられる。添加剤のそれぞれは、一種を単独で又は二種以上を組み合わせて使用することができる。 (Optional component)
The slurry according to the present embodiment may further contain an optional additive. Examples of the optional additive include a material having a carboxyl group (excluding a compound corresponding to a polyoxyalkylene compound or a water-soluble polymer), a polyoxyalkylene compound, a water-soluble polymer, an oxidizing agent (for example, hydrogen peroxide), and a dispersion. Agents (for example, phosphoric acid-based inorganic salts). Each of the additives can be used alone or in combination of two or more.
　カルボキシル基を有する材料としては、酢酸、プロピオン酸、酪酸、吉草酸等のモノカルボン酸；乳酸、リンゴ酸、クエン酸等のヒドロキシ酸；マロン酸、コハク酸、フマル酸、マレイン酸等のジカルボン酸；ポリアクリル酸、ポリマレイン酸等のポリカルボン酸；アルギニン、ヒスチジン、リシン等のアミノ酸などが挙げられる。 Examples of the material having a carboxyl group include monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and valeric acid; hydroxy acids such as lactic acid, malic acid, and citric acid; and dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, and maleic acid. Polycarboxylic acids such as polyacrylic acid and polymaleic acid; and amino acids such as arginine, histidine and lysine.
　ポリオキシアルキレン化合物としては、ポリアルキレングリコール、ポリオキシアルキレン誘導体等が挙げられる。 Polyoxyalkylene compounds include polyalkylene glycols, polyoxyalkylene derivatives and the like.
　ポリアルキレングリコールとしては、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール等が挙げられる。ポリアルキレングリコールとしては、ポリエチレングリコール及びポリプロピレングリコールからなる群より選択される少なくとも一種が好ましく、ポリエチレングリコールがより好ましい。 Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polybutylene glycol and the like. As the polyalkylene glycol, at least one selected from the group consisting of polyethylene glycol and polypropylene glycol is preferable, and polyethylene glycol is more preferable.
　ポリオキシアルキレン誘導体は、例えば、ポリアルキレングリコールに官能基若しくは置換基を導入した化合物、又は、有機化合物にポリアルキレンオキシドを付加した化合物である。前記官能基又は置換基としては、例えば、アルキルエーテル基、アルキルフェニルエーテル基、フェニルエーテル基、スチレン化フェニルエーテル基、グリセリルエーテル基、アルキルアミン基、脂肪酸エステル基、及び、グリコールエステル基が挙げられる。ポリオキシアルキレン誘導体としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンビスフェノールエーテル（例えば、日本乳化剤株式会社製、ＢＡグリコールシリーズ）、ポリオキシエチレンスチレン化フェニルエーテル（例えば、花王株式会社製、エマルゲンシリーズ）、ポリオキシエチレンアルキルフェニルエーテル（例えば、第一工業製薬株式会社製、ノイゲンＥＡシリーズ）、ポリオキシアルキレンポリグリセリルエーテル（例えば、阪本薬品工業株式会社製、ＳＣ－Ｅシリーズ及びＳＣ－Ｐシリーズ）、ポリオキシエチレンソルビタン脂肪酸エステル（例えば、第一工業製薬株式会社製、ソルゲンＴＷシリーズ）、ポリオキシエチレン脂肪酸エステル（例えば、花王株式会社製、エマノーンシリーズ）、ポリオキシエチレンアルキルアミン（例えば、第一工業製薬株式会社製、アミラヂンＤ）、並びに、ポリアルキレンオキシドを付加したその他の化合物（例えば、日信化学工業株式会社製、サーフィノール４６５、及び、日本乳化剤株式会社製、ＴＭＰシリーズ）が挙げられる。 The polyoxyalkylene derivative is, for example, a compound obtained by introducing a functional group or a substituent into polyalkylene glycol, or a compound obtained by adding a polyalkylene oxide to an organic compound. Examples of the functional group or the substituent include an alkyl ether group, an alkyl phenyl ether group, a phenyl ether group, a styrenated phenyl ether group, a glyceryl ether group, an alkylamine group, a fatty acid ester group, and a glycol ester group. . Examples of the polyoxyalkylene derivative include polyoxyethylene alkyl ether, polyoxyethylene bisphenol ether (for example, BA glycol series manufactured by Nippon Emulsifier Co., Ltd.), and polyoxyethylene styrenated phenyl ether (for example, Emulgen manufactured by Kao Corporation) Series), polyoxyethylene alkylphenyl ether (eg, Neugen EA series manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyalkylene polyglyceryl ether (eg, SC-E series and SC-P series manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) Polyoxyethylene sorbitan fatty acid ester (for example, Daiichi Kogyo Seiyaku Co., Ltd., Sorgen TW series), polyoxyethylene fatty acid ester (for example, Kao Corporation, Emanon series), Lioxyethylene alkylamine (for example, Amiradin D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and other compounds to which polyalkylene oxide is added (for example, Nippon Chemical Industries, Ltd., Surfynol 465, and Nippon Emulsifier) Co., Ltd., TMP series).
　「水溶性高分子」とは、水１００ｇに対して０．１ｇ以上溶解する高分子として定義する。前記ポリオキシアルキレン化合物に該当する高分子は「水溶性高分子」に含まれないものとする。水溶性高分子としては、特に制限はなく、ポリアクリルアミド、ポリジメチルアクリルアミド等のアクリル系ポリマ；カルボキシメチルセルロース、寒天、カードラン、デキストリン、シクロデキストリン、プルラン等の多糖類；ポリビニルアルコール、ポリビニルピロリドン、ポリアクロレイン等のビニル系ポリマ；ポリグリセリン、ポリグリセリン誘導体等のグリセリン系ポリマ；ポリエチレングリコールなどが挙げられる。 “Water-soluble polymer” is defined as a polymer that is soluble in 0.1 g or more in 100 g of water. The polymer corresponding to the polyoxyalkylene compound is not included in the “water-soluble polymer”. The water-soluble polymer is not particularly limited, and includes acrylic polymers such as polyacrylamide and polydimethylacrylamide; polysaccharides such as carboxymethylcellulose, agar, curdlan, dextrin, cyclodextrin, and pullulan; polyvinyl alcohol, polyvinylpyrrolidone, and polysaccharide. Vinyl-based polymers such as acrolein; glycerin-based polymers such as polyglycerin and polyglycerin derivatives; and polyethylene glycol.
（スラリの特性）
　本実施形態に係るスラリは、絶縁材料の研磨速度が向上する観点から、当該スラリを被研磨面に接触させることにより砥粒を被研磨面（基体の被研磨面等）に接触させたときに、金属Ｍの複数の価数の中で最も小さい価数の割合としてＸ線光電子分光法において０．１３以上を与える。前記価数の割合は、被研磨面に接触した砥粒（被研磨面上に存在する砥粒）の金属Ｍにおける価数の割合である。前記価数の割合は、金属Ｍの全量（全原子）を１とした場合の割合であり、対象の価数を有する原子の数の割合（単位：ａｔ％）である。前記価数の割合は、実施例に記載の方法により測定できる。Ｘ線光電子分光スペクトルのピーク位置は、化学シフトに起因して、価数に応じて異なる。一方、それぞれのピークの原子数と、ピークの面積とは比例する。従って、スペクトルの形状に基づき、各価数の原子の個数の比が得られる。金属Ｍの価数の調整方法としては、砥粒に酸化処理又は還元処理を施す方法等が挙げられる。酸化処理の方法としては、酸化作用を有する試薬で砥粒を処理する方法；空気中又は酸素雰囲気下で高温処理する方法等が挙げられる。還元処理の方法としては、還元作用を有する試薬で砥粒を処理する方法；水素等の還元雰囲気下で高温処理する方法などが挙げられる。 (Slurry characteristics)
From the viewpoint of improving the polishing rate of the insulating material, the slurry according to the present embodiment is obtained when the abrasive is brought into contact with the surface to be polished (such as the surface to be polished) by bringing the slurry into contact with the surface to be polished. In the X-ray photoelectron spectroscopy, 0.13 or more is given as the ratio of the smallest valence among the plurality of valences of the metal M. The ratio of the valence is the ratio of the valence in the metal M of the abrasive grains (the abrasive grains existing on the polished surface) in contact with the surface to be polished. The valence ratio is a ratio when the total amount (total atoms) of the metal M is 1, and is a ratio (unit: at%) of the number of atoms having a target valence. The valence ratio can be measured by the method described in Examples. The peak position of the X-ray photoelectron spectroscopy spectrum differs depending on the valence due to the chemical shift. On the other hand, the number of atoms in each peak is proportional to the peak area. Therefore, the ratio of the number of atoms of each valence is obtained based on the shape of the spectrum. Examples of a method for adjusting the valence of the metal M include a method of performing an oxidation treatment or a reduction treatment on the abrasive grains. Examples of the oxidizing method include a method of treating abrasive grains with a reagent having an oxidizing effect; and a method of performing high-temperature treatment in air or in an oxygen atmosphere. Examples of the method of the reduction treatment include a method of treating abrasive grains with a reagent having a reducing action; and a method of performing high-temperature treatment in a reducing atmosphere such as hydrogen.
　スラリを被研磨面に接触させることにより砥粒を被研磨面に接触させたときに、金属Ｍは、複数の価数を有していてよい。最も小さい価数は、例えば３価であってよい。 金属 When the abrasive particles are brought into contact with the surface to be polished by bringing the slurry into contact with the surface to be polished, the metal M may have a plurality of valences. The smallest valence may be, for example, trivalent.
　被研磨面は、珪素（Ｓｉ）、アルミニウム（Ａｌ）、コバルト（Ｃｏ）、銅（Ｃｕ）、ガリウム（Ｇａ）、ゲルマニウム（Ｇｅ）、ヒ素（Ａｓ）、ルテニウム（Ｒｕ）、インジウム（Ｉｎ）、スズ（Ｓｎ）、ハフニウム（Ｈｆ）、タリウム（Ｔａ）、タングステン（Ｗ）及び白金（Ｐｔ）からなる群より選ばれる少なくとも一種を含むことができる。被研磨面は、金属、合金、半導体、金属酸化物、金属窒化物、金属炭化物、金属リン化合物、金属ヒ素化合物、及び、有機化合物（例えばポリマー）からなる群より選ばれる少なくとも一種を含むことができる。被研磨面は、絶縁材料を含むことが可能であり、酸化珪素を含むことができる。 The surface to be polished is silicon (Si), aluminum (Al), cobalt (Co), copper (Cu), gallium (Ga), germanium (Ge), arsenic (As), ruthenium (Ru), indium (In), It can contain at least one selected from the group consisting of tin (Sn), hafnium (Hf), thallium (Ta), tungsten (W), and platinum (Pt). The surface to be polished may include at least one selected from the group consisting of metals, alloys, semiconductors, metal oxides, metal nitrides, metal carbides, metal phosphorus compounds, metal arsenic compounds, and organic compounds (eg, polymers). it can. The surface to be polished can include an insulating material and can include silicon oxide.
　被研磨面を有する基体としては、被研磨基板等が挙げられる。被研磨基板としては、例えば、半導体素子製造に係る基板（例えば、ＳＴＩパターン、ゲートパターン、配線パターン等が形成された半導体基板）上に被研磨材料が形成された基体が挙げられる。被研磨材料としては、絶縁材料（酸化珪素等）、金属などが挙げられる。被研磨材料は、単一の材料であってもよく、複数の材料であってもよい。複数の材料が被研磨面に露出している場合、それらを被研磨材料と見なすことができる。被研磨材料は、膜状（被研磨膜）であってもよく、絶縁膜（酸化珪素膜等）、金属膜などであってもよい。 基 体 Examples of the substrate having a surface to be polished include a substrate to be polished. Examples of the substrate to be polished include a substrate in which a material to be polished is formed on a substrate (for example, a semiconductor substrate on which an STI pattern, a gate pattern, a wiring pattern, and the like are formed) for manufacturing a semiconductor element. Examples of the material to be polished include an insulating material (such as silicon oxide) and a metal. The material to be polished may be a single material or a plurality of materials. When a plurality of materials are exposed on the surface to be polished, they can be regarded as the materials to be polished. The material to be polished may be a film (a film to be polished), an insulating film (such as a silicon oxide film), a metal film, or the like.
　砥粒を被研磨面に接触させた後における前記価数の割合は、絶縁材料の研磨速度が更に向上する観点から、０．１４以上が好ましく、０．１５以上がより好ましく、０．１６以上が更に好ましい。前記価数の割合は、１以下であってよく、０．８以下であってよい。 The ratio of the valence after the abrasive grains are brought into contact with the surface to be polished is preferably 0.14 or more, more preferably 0.15 or more, and 0.16 or more from the viewpoint of further improving the polishing rate of the insulating material. Is more preferred. The valence ratio may be 1 or less, and may be 0.8 or less.
　本実施形態に係るスラリのｐＨの下限は、絶縁材料の研磨速度が更に向上する観点から、２．０以上が好ましく、２．５以上がより好ましく、２．８以上が更に好ましく、３．０以上が特に好ましい。ｐＨの下限は、３．２以上であってよく、３．５以上であってよく、４．０以上であってよく、４．２以上であってよく、４．３以上であってよい。ｐＨの上限は、スラリの保存安定性が更に向上する観点から、７．０以下が好ましい。ｐＨの上限は、６．５以下であってよく、６．０以下であってよく、５．０以下であってよく、４．８以下であってよく、４．７以下であってよく、４．６以下であってよく、４．５以下であってよく、４．４以下であってよい。前記観点から、ｐＨは、２．０～７．０であることがより好ましい。スラリのｐＨは、液温２５℃におけるｐＨと定義する。 The lower limit of the pH of the slurry according to this embodiment is preferably 2.0 or more, more preferably 2.5 or more, still more preferably 2.8 or more, from the viewpoint of further improving the polishing rate of the insulating material. The above is particularly preferred. The lower limit of the pH may be not less than 3.2, not less than 3.5, not less than 4.0, not less than 4.2, and not less than 4.3. The upper limit of the pH is preferably 7.0 or less from the viewpoint of further improving the storage stability of the slurry. The upper limit of the pH may be 6.5 or less, may be 6.0 or less, may be 5.0 or less, may be 4.8 or less, may be 4.7 or less, It may be 4.6 or less, may be 4.5 or less, and may be 4.4 or less. From the above viewpoint, the pH is more preferably from 2.0 to 7.0. The pH of the slurry is defined as the pH at a liquid temperature of 25 ° C.
　スラリのｐＨは、無機酸、有機酸等の酸成分；アンモニア、水酸化ナトリウム、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、イミダゾール、アルカノールアミン等のアルカリ成分などによって調整できる。ｐＨを安定化させるため、緩衝剤を添加してもよい。緩衝液（緩衝剤を含む液）として緩衝剤を添加してもよい。このような緩衝液としては、酢酸塩緩衝液、フタル酸塩緩衝液等が挙げられる。 The pH of the slurry can be adjusted by an acid component such as an inorganic acid and an organic acid; and an alkaline component such as ammonia, sodium hydroxide, tetramethylammonium hydroxide (TMAH), imidazole and alkanolamine. A buffer may be added to stabilize the pH. A buffer may be added as a buffer (a solution containing a buffer). Examples of such a buffer include an acetate buffer, a phthalate buffer and the like.
　本実施形態に係るスラリのｐＨは、ｐＨメータ（例えば、東亜ディーケーケー株式会社製の型番ＰＨＬ－４０）で測定することができる。具体的には例えば、フタル酸塩ｐＨ緩衝液（ｐＨ：４．０１）及び中性リン酸塩ｐＨ緩衝液（ｐＨ：６．８６）を標準緩衝液として用いてｐＨメータを２点校正した後、ｐＨメータの電極をスラリに入れて、２分以上経過して安定した後の値を測定する。標準緩衝液及びスラリの液温は、共に２５℃とする。 ＰＨ The pH of the slurry according to the present embodiment can be measured with a pH meter (for example, model number PHL-40 manufactured by Toa DKK Ltd.). Specifically, for example, after two-point calibration of a pH meter using a phthalate pH buffer (pH: 4.01) and a neutral phosphate pH buffer (pH: 6.86) as a standard buffer, The electrode of the pH meter is put in the slurry, and the value is measured after 2 minutes or more have passed and stabilized. The temperature of both the standard buffer and the slurry is 25 ° C.
　本実施形態に係るスラリをＣＭＰ研磨液として用いる場合、研磨液の構成成分を一液式研磨液として保存してもよく、砥粒及び液状媒体を含むスラリ（第１の液）と、添加剤及び液状媒体を含む添加液（第２の液）とを混合して前記研磨液となるように前記研磨液の構成成分をスラリと添加液とに分けた複数液式（例えば二液式）の研磨液セットとして保存してもよい。添加液は、例えば酸化剤を含んでいてもよい。前記研磨液の構成成分は、三液以上に分けた研磨液セットとして保存してもよい。 When the slurry according to the present embodiment is used as a CMP polishing liquid, the constituent components of the polishing liquid may be stored as a one-part polishing liquid, and a slurry (a first liquid) containing abrasive grains and a liquid medium, and an additive And an additive liquid (second liquid) containing a liquid medium, and the constituent components of the polishing liquid are separated into a slurry and an additive liquid so that the polishing liquid becomes the polishing liquid. It may be stored as a polishing liquid set. The additive liquid may contain, for example, an oxidizing agent. The constituents of the polishing liquid may be stored as a polishing liquid set divided into three or more liquids.
　前記研磨液セットにおいては、研磨直前又は研磨時に、スラリ及び添加液が混合されて研磨液が作製される。また、一液式研磨液は、液状媒体の含有量を減じた研磨液用貯蔵液として保存されると共に、研磨時に液状媒体で希釈して用いられてもよい。複数液式の研磨液セットは、液状媒体の含有量を減じたスラリ用貯蔵液及び添加液用貯蔵液として保存されると共に、研磨時に液状媒体で希釈して用いられてもよい。 研磨 In the polishing liquid set, the slurry and the additive liquid are mixed immediately before or during polishing to prepare a polishing liquid. In addition, the one-component polishing liquid may be stored as a polishing liquid storage liquid in which the content of the liquid medium is reduced, and may be used after being diluted with the liquid medium during polishing. The plural-liquid type polishing liquid set may be stored as a storage liquid for slurry and a storage liquid for additive liquid in which the content of the liquid medium is reduced, and may be used after being diluted with the liquid medium during polishing.
＜スラリのスクリーニング方法＞
　本実施形態に係るスラリのスクリーニング方法（スラリの選択方法）は、砥粒及び液状媒体を含有するスラリを被研磨面（基体の被研磨面等）に接触させることにより前記砥粒を前記被研磨面に接触させる接触工程と、前記被研磨面に前記砥粒が接触した状態で、前記砥粒に含まれる金属の価数をＸ線光電子分光法により測定する測定工程と、を備え、前記砥粒が、金属酸化物及び金属水酸化物からなる群より選ばれる少なくとも一種の金属化合物を含み、前記金属化合物が、複数の価数を取り得る金属を含み、前記測定工程において、前記金属の前記複数の価数の中で最も小さい価数の割合を得る。本実施形態に係るスラリのスクリーニング方法では、絶縁材料の研磨速度を向上させることが可能なスラリを選定できる。 <Slurry screening method>
In the slurry screening method (slurry selection method) according to the present embodiment, the slurry containing the abrasive particles and the liquid medium is brought into contact with a surface to be polished (the surface to be polished, etc.) so that the abrasive particles are polished. A contact step of contacting the surface with the surface, and a measurement step of measuring the valence of metal contained in the abrasive particles by X-ray photoelectron spectroscopy in a state where the abrasive particles are in contact with the surface to be polished, The grains include at least one metal compound selected from the group consisting of metal oxides and metal hydroxides, wherein the metal compound includes a metal that can have a plurality of valences, and in the measurement step, Get the lowest valence ratio among multiple valences. In the slurry screening method according to the present embodiment, a slurry capable of improving the polishing rate of the insulating material can be selected.
　接触工程では、例えば、被研磨面を有する基体をスラリに浸漬させることによりスラリを被研磨面に接触させることができる。接触工程と測定工程との間に被研磨面を乾燥させてよい。 In the contact step, for example, the slurry can be brought into contact with the surface to be polished by immersing the substrate having the surface to be polished in the slurry. The surface to be polished may be dried between the contacting step and the measuring step.
　測定工程は、接触工程の後に行うことができる。測定工程におけるＸ線光電子分光法は、実施例に記載の方法により測定できる。 The measuring step can be performed after the contacting step. X-ray photoelectron spectroscopy in the measurement step can be measured by the method described in the examples.
　本実施形態に係るスラリのスクリーニング方法は、測定工程の後に、測定工程で得られた価数の割合を判定する判定工程を備えていてよい。判定工程では、例えば、価数の割合として０．１３以上を与えるスラリを選定する。 ス ラ The slurry screening method according to the present embodiment may include, after the measuring step, a determining step of determining the ratio of the valence obtained in the measuring step. In the determination step, for example, a slurry that gives a valence ratio of 0.13 or more is selected.
＜研磨方法＞
　本実施形態に係る研磨方法（基体の研磨方法等）は、本実施形態に係るスラリのスクリーニング方法の測定工程において得られる価数の割合として０．１３以上を与えるスラリを用いて被研磨面（基体の被研磨面等）を研磨する研磨工程を備えている。 <Polishing method>
The polishing method according to the present embodiment (such as a method for polishing a substrate) uses a slurry that gives 0.13 or more as a valence ratio obtained in the measurement step of the slurry screening method according to the present embodiment to the surface to be polished ( A polishing step of polishing the surface to be polished of the substrate).
　研磨工程では、例えば、被研磨材料を有する基体の当該被研磨材料を研磨定盤の研磨パッド（研磨布）に押圧した状態で、前記スラリを被研磨材料と研磨パッドとの間に供給し、基体と研磨定盤とを相対的に動かして被研磨材料の被研磨面を研磨する。研磨工程では、例えば、被研磨材料の少なくとも一部を研磨により除去する。被研磨材料（例えば、酸化珪素等の絶縁材料）を前記スラリで研磨し、余分な部分を除去することによって、被研磨材料の表面の凹凸を解消し、被研磨材料の表面全体にわたって平滑な面を得ることができる。 In the polishing step, for example, the slurry is supplied between the material to be polished and the polishing pad while the material to be polished of the substrate having the material to be polished is pressed against a polishing pad (polishing cloth) of a polishing platen. The substrate and the polishing platen are relatively moved to polish the surface to be polished of the material to be polished. In the polishing step, for example, at least a part of the material to be polished is removed by polishing. A material to be polished (for example, an insulating material such as silicon oxide) is polished with the slurry to remove an excess portion, thereby eliminating irregularities on the surface of the material to be polished, and providing a smooth surface over the entire surface of the material to be polished. Can be obtained.
　本実施形態に係る研磨方法において、研磨装置としては、被研磨面を有する基体を保持可能なホルダーと、研磨パッドを貼り付け可能な研磨定盤とを有する一般的な研磨装置を使用できる。ホルダー及び研磨定盤のそれぞれには、回転数が変更可能なモータ等が取り付けてある。研磨装置としては、例えば、株式会社荏原製作所製の研磨装置：Ｆ－ＲＥＸ３００、又は、ＡＰＰＬＩＥＤ　ＭＡＴＥＲＩＡＬＳ社製の研磨装置：ＭＩＲＲＡを使用できる。 In the polishing method according to the present embodiment, a general polishing apparatus having a holder capable of holding a substrate having a surface to be polished and a polishing platen to which a polishing pad can be attached can be used as the polishing apparatus. Each of the holder and the polishing table is provided with a motor or the like whose rotation speed can be changed. As the polishing apparatus, for example, a polishing apparatus: F-REX300 manufactured by Ebara Corporation or a polishing apparatus: MIRRA manufactured by APPLIED @ MATERIALS can be used.
　研磨パッドとしては、一般的な不織布、発泡体、非発泡体等が使用できる。研磨パッドの材質としては、ポリウレタン、アクリル樹脂、ポリエステル、アクリル－エステル共重合体、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレン、ポリ４－メチルペンテン、セルロース、セルロースエステル、ポリアミド（例えば、ナイロン（商標名）及びアラミド）、ポリイミド、ポリイミドアミド、ポリシロキサン共重合体、オキシラン化合物、フェノール樹脂、ポリスチレン、ポリカーボネート、エポキシ樹脂等の樹脂が使用できる。研磨パッドの材質としては、特に、研磨速度及び平坦性に更に優れる観点から、発泡ポリウレタン及び非発泡ポリウレタンからなる群より選択される少なくとも一種が好ましい。研磨パッドには、スラリがたまるような溝加工が施されていることが好ましい。 As the polishing pad, a general nonwoven fabric, foam, non-foam, or the like can be used. Examples of the material of the polishing pad include polyurethane, acrylic resin, polyester, acrylic-ester copolymer, polytetrafluoroethylene, polypropylene, polyethylene, poly4-methylpentene, cellulose, cellulose ester, polyamide (eg, nylon (trade name)) And aramid), polyimide, polyimide amide, polysiloxane copolymer, oxirane compound, phenol resin, polystyrene, polycarbonate, epoxy resin and the like. The material of the polishing pad is preferably at least one selected from the group consisting of foamed polyurethane and non-foamed polyurethane, particularly from the viewpoint of further improving the polishing rate and flatness. The polishing pad is preferably provided with a groove processing for accumulating slurry.
　研磨条件に制限はないが、研磨定盤の回転速度の上限は、基体が飛び出さないように２００ｍｉｎ－１（ｍｉｎ－１＝ｒｐｍ）以下が好ましく、基体にかける研磨圧力（加工荷重）の上限は、研磨傷が発生することを抑制しやすい観点から、１００ｋＰａ以下が好ましい。研磨している間、ポンプ等で連続的にスラリを研磨パッドに供給することが好ましい。この供給量に制限はないが、研磨パッドの表面が常にスラリで覆われていることが好ましい。 Although there is no limit to the polishing conditions, the upper limit of the rotational speed of the polishing platen is preferably 200min -1 (min -1 = rpm) or less so as not fly out is base, the upper limit of the polishing pressure (working load) applied to the substrate Is preferably 100 kPa or less from the viewpoint of easily suppressing generation of polishing scratches. It is preferable that the slurry be continuously supplied to the polishing pad by a pump or the like during polishing. The supply amount is not limited, but it is preferable that the surface of the polishing pad is always covered with the slurry.
　本実施形態は、酸化珪素を含む被研磨面を研磨するために使用されることが好ましい。本実施形態によれば、酸化珪素を含む被研磨面の研磨へのスラリの使用を提供することができる。本実施形態は、ＳＴＩの形成及び層間絶縁材料の高速研磨に好適に使用できる。絶縁材料（例えば酸化珪素）の研磨速度の下限は、７０ｎｍ／ｍｉｎ以上が好ましく、１００ｎｍ／ｍｉｎ以上がより好ましく、１５０ｎｍ／ｍｉｎ以上が更に好ましく、１８０ｎｍ／ｍｉｎ以上が特に好ましく、２００ｎｍ／ｍｉｎ以上が極めて好ましい。 This embodiment is preferably used for polishing a surface to be polished containing silicon oxide. According to the present embodiment, it is possible to provide use of a slurry for polishing a surface to be polished including silicon oxide. The present embodiment can be suitably used for forming an STI and for high-speed polishing of an interlayer insulating material. The lower limit of the polishing rate of the insulating material (for example, silicon oxide) is preferably at least 70 nm / min, more preferably at least 100 nm / min, further preferably at least 150 nm / min, particularly preferably at least 180 nm / min, and preferably at least 200 nm / min. Very preferred.
　本実施形態は、プリメタル絶縁材料の研磨にも使用できる。プリメタル絶縁材料としては、酸化珪素、リン－シリケートガラス、ボロン－リン－シリケートガラス、シリコンオキシフロリド、フッ化アモルファスカーボン等が挙げられる。 This embodiment can also be used for polishing a premetal insulating material. Examples of the premetal insulating material include silicon oxide, phosphorus-silicate glass, boron-phosphorus-silicate glass, silicon oxyfluoride, and amorphous carbon fluoride.
　本実施形態は、酸化珪素等の絶縁材料以外の材料にも適用できる。このような材料としては、Ｈｆ系、Ｔｉ系、Ｔａ系酸化物等の高誘電率材料；シリコン、アモルファスシリコン、ＳｉＣ、ＳｉＧｅ、Ｇｅ、ＧａＮ、ＧａＰ、ＧａＡｓ、有機半導体等の半導体材料；ＧｅＳｂＴｅ等の相変化材料；ＩＴＯ等の無機導電材料；ポリイミド系、ポリベンゾオキサゾール系、アクリル系、エポキシ系、フェノール系等のポリマ樹脂材料などが挙げられる。 This embodiment can be applied to materials other than insulating materials such as silicon oxide. Examples of such materials include high dielectric constant materials such as Hf-based, Ti-based, and Ta-based oxides; semiconductor materials such as silicon, amorphous silicon, SiC, SiGe, Ge, GaN, GaP, GaAs, and organic semiconductors; and GeSbTe. Phase change materials; inorganic conductive materials such as ITO; and polymer resin materials such as polyimide, polybenzoxazole, acrylic, epoxy, and phenol.
　本実施形態は、膜状の研磨対象だけでなく、ガラス、シリコン、ＳｉＣ、ＳｉＧｅ、Ｇｅ、ＧａＮ、ＧａＰ、ＧａＡｓ、サファイヤ、プラスチック等から構成される各種基板にも適用できる。 The present embodiment is applicable not only to a film-shaped polishing target but also to various substrates made of glass, silicon, SiC, SiGe, Ge, GaN, GaP, GaAs, sapphire, plastic, or the like.
　本実施形態は、半導体素子の製造だけでなく、ＴＦＴ、有機ＥＬ等の画像表示装置；フォトマスク、レンズ、プリズム、光ファイバー、単結晶シンチレータ等の光学部品；光スイッチング素子、光導波路等の光学素子；固体レーザ、青色レーザＬＥＤ等の発光素子；磁気ディスク、磁気ヘッド等の磁気記憶装置などの製造に用いることができる。 This embodiment is applicable not only to the manufacture of semiconductor elements, but also to image display devices such as TFTs and organic ELs; optical components such as photomasks, lenses, prisms, optical fibers, and single-crystal scintillators; A light-emitting element such as a solid-state laser or a blue laser LED; and a light-emitting element such as a magnetic disk or a magnetic head.
　以下、本発明を実施例に基づいて具体的に説明するが、本発明は下記実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples.
＜セリウム酸化物スラリの準備＞
　セリウム酸化物を含む粒子（第１の粒子。以下、「セリウム酸化物粒子」という）と、和光純薬工業株式会社製の商品名：リン酸二水素アンモニウム（分子量：９７．９９）とを混合して、セリウム酸化物粒子を５．０質量％（固形分含量）含有するセリウム酸化物スラリ（ｐＨ：７）を調製した。リン酸二水素アンモニウムの配合量は、セリウム酸化物粒子の全量を基準として１質量％に調整した。 <Preparation of cerium oxide slurry>
Particles containing cerium oxide (first particles; hereinafter, referred to as “cerium oxide particles”) mixed with ammonium dihydrogen phosphate (molecular weight: 97.99) manufactured by Wako Pure Chemical Industries, Ltd. Thus, a cerium oxide slurry (pH: 7) containing 5.0% by mass (solid content) of cerium oxide particles was prepared. The amount of ammonium dihydrogen phosphate was adjusted to 1% by mass based on the total amount of cerium oxide particles.
　マイクロトラック・ベル株式会社製の商品名：マイクロトラックＭＴ３３００ＥＸＩＩ内にセリウム酸化物スラリを適量投入し、セリウム酸化物粒子の平均粒径を測定した。表示された平均粒径値を平均粒径（平均二次粒径）として得た。セリウム酸化物スラリにおけるセリウム酸化物粒子の平均粒径は１４５ｎｍであった。 @ Trade name of Microtrac Bell Co., Ltd .: An appropriate amount of cerium oxide slurry was charged into Microtrac MT3300EXII, and the average particle size of the cerium oxide particles was measured. The indicated average particle size value was obtained as the average particle size (average secondary particle size). The average particle size of the cerium oxide particles in the cerium oxide slurry was 145 nm.
　ベックマン・コールター株式会社製の商品名：ＤｅｌｓａＮａｎｏ　Ｃ内に適量のセリウム酸化物スラリを投入し、２５℃において測定を２回行った。表示されたゼータ電位の平均値をゼータ電位として得た。セリウム酸化物スラリにおけるセリウム酸化物粒子のゼータ電位は－５５ｍＶであった。 An appropriate amount of cerium oxide slurry was charged into Beckman Coulter Co., Ltd. trade name: DelsaNano @ C, and the measurement was performed twice at 25 ° C. The average value of the indicated zeta potential was obtained as the zeta potential. The zeta potential of the cerium oxide particles in the cerium oxide slurry was -55 mV.
＜セリウム水酸化物スラリの準備＞
（セリウム水酸化物の合成）
　４８０ｇのＣｅ（ＮＨ４）２（ＮＯ３）６５０質量％水溶液（日本化学産業株式会社製、商品名：ＣＡＮ５０液）を７４５０ｇの純水と混合して溶液を得た。次いで、この溶液を撹拌しながら、７５０ｇのイミダゾール水溶液（１０質量％水溶液、１．４７ｍｏｌ／Ｌ）を５ｍＬ／ｍｉｎの混合速度で滴下して、セリウム水酸化物を含む沈殿物を得た。セリウム水酸化物の合成は、温度２０℃、撹拌速度５００ｍｉｎ－１で行った。撹拌は、羽根部全長５ｃｍの３枚羽根ピッチパドルを用いて行った。 <Preparation of cerium hydroxide slurry>
(Synthesis of cerium hydroxide)
480 g of a 50% by mass aqueous solution of Ce (NH 4 ) 2 (NO 3 ) 6 (manufactured by Nippon Chemical Industry Co., Ltd., trade name: CAN 50 solution) was mixed with 7450 g of pure water to obtain a solution. Next, while stirring this solution, 750 g of an imidazole aqueous solution (10% by mass aqueous solution, 1.47 mol / L) was added dropwise at a mixing speed of 5 mL / min to obtain a precipitate containing cerium hydroxide. The synthesis of cerium hydroxide was performed at a temperature of 20 ° C. and a stirring speed of 500 min −1 . Stirring was performed using a three-blade pitch paddle having a blade length of 5 cm.
　得られた沈殿物（セリウム水酸化物を含む沈殿物）を遠心分離（４０００ｍｉｎ－１、５分間）した後にデカンテーションで液相を除去することによって固液分離を施した。固液分離により得られた粒子１０ｇと、水９９０ｇと、を混合した後、超音波洗浄機を用いて粒子を水に分散させて、セリウム水酸化物を含む粒子（第２の粒子。以下、「セリウム水酸化物粒子」という）を含有するセリウム水酸化物スラリ（粒子の含有量：１．０質量％）を調製した。 The obtained precipitate (precipitate containing cerium hydroxide) was centrifuged (4000 min -1 , 5 minutes), and then the liquid phase was removed by decantation to perform solid-liquid separation. After mixing 10 g of the particles obtained by the solid-liquid separation and 990 g of water, the particles are dispersed in water using an ultrasonic cleaner, and the particles containing cerium hydroxide (second particles; hereinafter, referred to as “second particles”). A cerium hydroxide slurry containing “cerium hydroxide particles” (particle content: 1.0% by mass) was prepared.
（平均粒径の測定）
　ベックマン・コールター株式会社製、商品名：Ｎ５を用いてセリウム水酸化物スラリにおけるセリウム水酸化物粒子の平均粒径（平均二次粒径）を測定したところ、１０ｎｍであった。測定法は次のとおりである。まず、１．０質量％のセリウム水酸化物粒子を含む測定サンプル（セリウム水酸化物スラリ。水分散液）を１ｃｍ角のセルに約１ｍＬ入れた後、Ｎ５内にセルを設置した。Ｎ５のソフトの測定サンプル情報の屈折率を１．３３３、粘度を０．８８７ｍＰａ・ｓに設定し、２５℃において測定を行い、Ｕｎｉｍｏｄａｌ　Ｓｉｚｅ　Ｍｅａｎとして表示される値を読み取った。 (Measurement of average particle size)
The average particle size (average secondary particle size) of the cerium hydroxide particles in the cerium hydroxide slurry was measured using a trade name: N5 manufactured by Beckman Coulter KK and found to be 10 nm. The measuring method is as follows. First, about 1 mL of a measurement sample (cerium hydroxide slurry; aqueous dispersion) containing 1.0% by mass of cerium hydroxide particles was placed in a 1 cm square cell, and then the cell was placed in N5. The refractive index of the measurement sample information of N5 software was set to 1.333, the viscosity was set to 0.887 mPa · s, the measurement was performed at 25 ° C., and the value indicated as Unimodal Size Mean was read.
（ゼータ電位の測定）
　ベックマン・コールター株式会社製の商品名：ＤｅｌｓａＮａｎｏ　Ｃ内に適量のセリウム水酸化物スラリを投入し、２５℃において測定を２回行った。表示されたゼータ電位の平均値をゼータ電位として得た。セリウム水酸化物スラリにおけるセリウム水酸化物粒子のゼータ電位は＋５０ｍＶであった。 (Measurement of zeta potential)
An appropriate amount of cerium hydroxide slurry was charged into DelsaNano C (trade name, manufactured by Beckman Coulter, Inc.), and the measurement was performed twice at 25 ° C. The average value of the indicated zeta potential was obtained as the zeta potential. The zeta potential of the cerium hydroxide particles in the cerium hydroxide slurry was +50 mV.
（セリウム水酸化物粒子の構造分析）
　セリウム水酸化物スラリを適量採取し、真空乾燥してセリウム水酸化物粒子を単離した後に純水で充分に洗浄して試料を得た。得られた試料について、ＦＴ－ＩＲ　ＡＴＲ法による測定を行ったところ、水酸化物イオン（ＯＨ－）に基づくピークの他に、硝酸イオン（ＮＯ３ －）に基づくピークが観測された。また、同試料について、窒素に対するＸＰＳ（Ｎ－ＸＰＳ）測定を行ったところ、ＮＨ４ ＋に基づくピークは観測されず、硝酸イオンに基づくピークが観測された。これらの結果より、セリウム水酸化物粒子は、セリウム元素に結合した硝酸イオンを有する粒子を少なくとも一部含有することが確認された。また、セリウム元素に結合した水酸化物イオンを有する粒子がセリウム水酸化物粒子の少なくとも一部に含有されることから、セリウム水酸化物粒子がセリウム水酸化物を含有することが確認された。これらの結果より、セリウムの水酸化物が、セリウム元素に結合した水酸化物イオンを含むことが確認された。 (Structural analysis of cerium hydroxide particles)
An appropriate amount of cerium hydroxide slurry was sampled, vacuum-dried to isolate cerium hydroxide particles, and then sufficiently washed with pure water to obtain a sample. When the obtained sample was measured by the FT-IR ATR method, a peak based on nitrate ion (NO 3 − ) was observed in addition to a peak based on hydroxide ion (OH − ). When XPS (N-XPS) measurement of nitrogen was performed on the same sample, a peak based on NH 4 + was not observed but a peak based on nitrate ion was observed. From these results, it was confirmed that the cerium hydroxide particles at least partially contained particles having nitrate ions bonded to the cerium element. Further, since the particles having hydroxide ions bonded to the cerium element are contained in at least a part of the cerium hydroxide particles, it was confirmed that the cerium hydroxide particles contained cerium hydroxide. From these results, it was confirmed that the cerium hydroxide contained hydroxide ions bonded to the cerium element.
＜ＣＭＰスラリの調製＞
（実施例１）
　２枚羽根の撹拌羽根を用いて３００ｒｐｍの回転数で撹拌しながら、前記セリウム水酸化物スラリと、イオン交換水とを混合して混合液を得た。続いて、前記混合液を撹拌しながら前記セリウム酸化物スラリを前記混合液に混合した後、株式会社エスエヌディ製の超音波洗浄機（装置名：ＵＳ－１０５）を用いて超音波を照射しながら撹拌した。これにより、セリウム酸化物粒子と、当該セリウム酸化物粒子に接触したセリウム水酸化物粒子と、を含む複合粒子を含有するＣＭＰスラリを調製した。ＣＭＰスラリにおける砥粒の含有量（総量）は０．２質量％であり、セリウム酸化物粒子及びセリウム水酸化物粒子の質量比は１０：１（酸化物：水酸化物）であった。 <Preparation of CMP slurry>
(Example 1)
The cerium hydroxide slurry and the ion-exchanged water were mixed while stirring at a rotation speed of 300 rpm using two stirring blades to obtain a mixed solution. Subsequently, the cerium oxide slurry was mixed with the mixture while stirring the mixture, and then the mixture was irradiated with an ultrasonic wave using an ultrasonic cleaner (device name: US-105) manufactured by SND Corporation. Stirred. Thus, a CMP slurry containing composite particles containing cerium oxide particles and cerium hydroxide particles in contact with the cerium oxide particles was prepared. The content (total amount) of the abrasive grains in the CMP slurry was 0.2% by mass, and the mass ratio of the cerium oxide particles and the cerium hydroxide particles was 10: 1 (oxide: hydroxide).
（実施例２）
　２枚羽根の撹拌羽根を用いて３００ｒｐｍの回転数で撹拌しながら前記セリウム水酸化物スラリ４００ｇとイオン交換水１６００ｇとを混合した後、株式会社エスエヌディ製の超音波洗浄機（装置名：ＵＳ－１０５）を用いて超音波を照射しながら撹拌した。これにより、セリウム水酸化物粒子を含有するＣＭＰスラリ（セリウム水酸化物粒子の含有量：０．２質量％）を調製した。 (Example 2)
After mixing 400 g of the cerium hydroxide slurry and 1600 g of ion-exchanged water while stirring at a rotation speed of 300 rpm using a two-blade stirring blade, an ultrasonic cleaner (device name: US- The mixture was stirred while irradiating ultrasonic waves by using (105). As a result, a CMP slurry containing cerium hydroxide particles (content of cerium hydroxide particles: 0.2% by mass) was prepared.
（実施例３）
　砥粒としてセリア粒子（実施例１のセリウム酸化物粒子とは異なるセリウム酸化物粒子Ａ）を準備した。セリア粒子とイオン交換水とを混合することによりＣＭＰスラリ（砥粒の含有量：０．２質量％）を調製した。 (Example 3)
Ceria particles (cerium oxide particles A different from the cerium oxide particles of Example 1) were prepared as abrasive grains. A CMP slurry (content of abrasive grains: 0.2% by mass) was prepared by mixing ceria particles and ion-exchanged water.
（実施例４）
　砥粒としてセリア粒子（実施例１のセリウム酸化物粒子及びセリウム酸化物粒子Ａとは異なるセリウム酸化物粒子Ｂ）を準備した。セリア粒子とイオン交換水とを混合することによりＣＭＰスラリ（砥粒の含有量：０．２質量％）を調製した。 (Example 4)
Ceria particles (cerium oxide particles B and cerium oxide particles B different from cerium oxide particles A of Example 1) were prepared as abrasive grains. A CMP slurry (content of abrasive grains: 0.2% by mass) was prepared by mixing ceria particles and ion-exchanged water.
（比較例１）
　砥粒としてセリア粒子（実施例１のセリウム酸化物粒子及びセリウム酸化物粒子Ａ，Ｂとは異なるセリウム酸化物粒子Ｃ）を準備した。セリア粒子とイオン交換水とを混合することによりＣＭＰスラリ（砥粒の含有量：０．２質量％）を調製した。 (Comparative Example 1)
Ceria particles (cerium oxide particles of Example 1 and cerium oxide particles C different from cerium oxide particles A and B) were prepared as abrasive grains. A CMP slurry (content of abrasive grains: 0.2% by mass) was prepared by mixing ceria particles and ion-exchanged water.
（比較例２）
　前記セリウム水酸化物スラリを乾燥した後にセリウム水酸化物粒子を１８０℃で２４時間保持した。次に、このセリウム水酸化物粒子とイオン交換水とを混合した。これにより、砥粒としてセリウム水酸化物粒子を含有するＣＭＰスラリ（砥粒の含有量：０．２質量％）を調製した。 (Comparative Example 2)
After drying the cerium hydroxide slurry, the cerium hydroxide particles were kept at 180 ° C. for 24 hours. Next, the cerium hydroxide particles and ion-exchanged water were mixed. Thus, a CMP slurry containing cerium hydroxide particles as abrasive grains (abrasive grain content: 0.2% by mass) was prepared.
＜価数の測定＞
　ベックマン・コールター株式会社製の遠心分離機（商品名：Ｏｐｔｉｍａ　ＭＡＸ－ＴＬ）を用いてＣＭＰスラリ（砥粒の含有量：０．２質量％）を遠心加速度１．１×１０４Ｇで３０分間処理することにより固相及び液相（上澄み液）を分離した。液相を除去した後、固相を２５℃で２４時間真空乾燥することにより測定試料を得た。この測定試料中の砥粒に含まれるセリウムの価数ＡをＸ線光電子分光法により測定した。 <Measurement of valence>
Using a centrifuge (trade name: Optima MAX-TL) manufactured by Beckman Coulter KK, a CMP slurry (content of abrasive grains: 0.2% by mass) was centrifuged at a centrifugal acceleration of 1.1 × 10 4 G for 30 minutes. By the treatment, a solid phase and a liquid phase (supernatant) were separated. After removing the liquid phase, the solid phase was vacuum-dried at 25 ° C. for 24 hours to obtain a measurement sample. The valence A of cerium contained in the abrasive grains in this measurement sample was measured by X-ray photoelectron spectroscopy.
　次に、パターンが形成されていないブランケットウエハとして、プラズマＣＶＤ法で形成された厚さ２μｍの酸化珪素膜（ＳｉＯ２膜）をシリコン基板上に有する被研磨基板を準備した。ＣＭＰスラリ（砥粒の含有量：０．２質量％）に被研磨基板を１分間浸漬させた。続いて、被研磨基板をＣＭＰスラリから取り出した後、被研磨基板を窒素ガンで乾燥させた。そして、被研磨基板の被研磨面上に存在する砥粒に含まれるセリウムの価数ＢをＸ線光電子分光法により測定した。 Next, as a blanket wafer on which no pattern was formed, a substrate to be polished having a silicon oxide film (SiO 2 film) having a thickness of 2 μm formed by a plasma CVD method on a silicon substrate was prepared. The substrate to be polished was immersed in a CMP slurry (content of abrasive grains: 0.2% by mass) for 1 minute. Subsequently, after removing the substrate to be polished from the CMP slurry, the substrate to be polished was dried with a nitrogen gun. Then, the valence B of cerium contained in the abrasive grains present on the surface to be polished of the substrate to be polished was measured by X-ray photoelectron spectroscopy.
　Ｘ線光電子分光法（ＸＰＳ）の測定装置としてサーモフィッシャーサイエンティフィック製の商品名「Ｋ－Ａｌｐｈａ」を用いた。測定条件は以下のとおりである。
［ＸＰＳ条件］
　パスエネルギー：１００ｅＶ
　積算回数：１０回
　結合エネルギー：８７０～９３０ｅＶの範囲
　励起Ｘ線：ｍｏｎｏｃｈｒｏｍａｔｉｃ　Ａｌ　Ｋα１，２線（１４８６．６ｅＶ）
　Ｘ線径：２００μｍ
　光電子脱出角度：４５° As a measuring device for X-ray photoelectron spectroscopy (XPS), "K-Alpha" (trade name, manufactured by Thermo Fisher Scientific) was used. The measurement conditions are as follows.
[XPS conditions]
Pass energy: 100 eV
Number of integration: 10 times Binding energy: 870 to 930 eV Excitation X-ray: monochromatic Al Kα1,2 line (1486.6 eV)
X-ray diameter: 200 μm
Photoelectron escape angle: 45 °
　次に、セリウムの価数Ａ及び価数Ｂについて、装置に付属の解析ソフトを用いて、３価に起因する波形と、４価に起因する波形とを分離した。波形分離は、文献「Ｓｕｒｆａｃｅ　Ｓｃｉｅｎｃｅ　ｖｏｌ．５６３（２００４）ｐ．７４－８２」に記載の方法に準じて行った。そして、下記式に基づき３価の割合を求めた。測定結果を表１に示す。
　３価の割合　＝　（３価の量［ａｔ％］／（３価の量［ａｔ％］＋４価の量［ａｔ％］） Next, with respect to valence A and valence B of cerium, a waveform derived from trivalent and a waveform derived from tetravalent were separated using analysis software attached to the apparatus. Waveform separation was performed according to the method described in the document “Surface Science vol. 563 (2004) pp. 74-82”. Then, the trivalent ratio was determined based on the following equation. Table 1 shows the measurement results.
Trivalent ratio = (trivalent amount [at%] / (trivalent amount [at%] + tetravalent amount [at%])
＜ｐＨの測定＞
　ＣＭＰスラリのｐＨを東亜ディーケーケー株式会社製の型番ＰＨＬ－４０を用いて測定した。測定結果を表１に示す。 <Measurement of pH>
The pH of the CMP slurry was measured using a model number PHL-40 manufactured by Toa DKK Corporation. Table 1 shows the measurement results.
＜ゼータ電位の測定＞
　ベックマン・コールター株式会社製の商品名「ＤｅｌｓａＮａｎｏ　Ｃ」内に適量のＣＭＰスラリを投入した。２５℃において測定を２回行い、表示されたゼータ電位の平均値を採用した。測定結果を表１に示す。 <Measurement of zeta potential>
An appropriate amount of CMP slurry was put into a trade name “DelsaNano C” manufactured by Beckman Coulter, Inc. The measurement was performed twice at 25 ° C., and the average value of the displayed zeta potential was adopted. Table 1 shows the measurement results.
＜砥粒の平均粒径の測定＞
　マイクロトラック・ベル株式会社製の商品名：マイクロトラックＭＴ３３００ＥＸＩＩ内に実施例１、４の各ＣＭＰスラリ（砥粒の含有量：０．２質量％）を適量投入し、砥粒の平均粒径の測定を行った。また、ベックマン・コールター株式会社製の商品名：Ｎ５内に実施例２、３及び比較例１、２の各ＣＭＰスラリ（砥粒の含有量：０．２質量％）を適量投入し、砥粒の平均粒径の測定を行った。表示された平均粒径値を砥粒の平均粒径（平均二次粒径）として得た。測定結果を表１に示す。 <Measurement of average grain size of abrasive grains>
A trade name of Microtrac Bell Co., Ltd .: An appropriate amount of each of the CMP slurries of Examples 1 and 4 (the content of the abrasives: 0.2% by mass) was introduced into Microtrac MT3300EXII, A measurement was made. In addition, an appropriate amount of each of the CMP slurries of Examples 2, 3 and Comparative Examples 1 and 2 (content of abrasive grains: 0.2% by mass) was charged into N5 (trade name, manufactured by Beckman Coulter, Inc.). Was measured. The indicated average particle size value was obtained as the average particle size of the abrasive grains (average secondary particle size). Table 1 shows the measurement results.
＜研磨速度の測定＞
　上述の各ＣＭＰスラリ（砥粒の含有量：０．２質量％）を用いて、下記研磨条件で、上述の価数の評価で用いた被研磨基板を研磨した。
［ＣＭＰ研磨条件］
　研磨装置：ＭＩＲＲＡ（ＡＰＰＬＩＥＤ　ＭＡＴＥＲＩＡＬＳ社製）
　ＣＭＰスラリの流量：２００ｍＬ／ｍｉｎ
　研磨パッド：独立気泡を有する発泡ポリウレタン樹脂（ダウ・ケミカル日本株式会社製、型番ＩＣ１０１０）
　研磨圧力：１３ｋＰａ（２．０ｐｓｉ）
　被研磨基板及び研磨定盤の回転数：被研磨基板／研磨定盤＝９３／８７ｒｐｍ
　研磨時間：１ｍｉｎ
　ウエハの洗浄：ＣＭＰ処理後、超音波を印加しながら水で洗浄し、さらに、スピンドライヤで乾燥させた。 <Measurement of polishing rate>
The substrate to be polished used in the evaluation of the valence described above was polished under the following polishing conditions using each of the above-mentioned CMP slurries (content of abrasive grains: 0.2 mass%).
[CMP polishing conditions]
Polishing device: MIRRA (manufactured by APPLIED MATERIALS)
Flow rate of CMP slurry: 200 mL / min
Polishing pad: foamed polyurethane resin having closed cells (model number IC1010, manufactured by Dow Chemical Japan Co., Ltd.)
Polishing pressure: 13 kPa (2.0 psi)
Number of rotations of substrate to be polished and polishing platen: substrate to be polished / polishing platen = 93/87 rpm
Polishing time: 1 min
Cleaning of wafer: After the CMP treatment, the wafer was washed with water while applying ultrasonic waves, and further dried with a spin drier.
　前記条件で研磨及び洗浄した酸化珪素膜の研磨速度（ＳｉＯ２ＲＲ）を下記式より求めた。測定結果を表１に示す。研磨前後における酸化珪素膜の膜厚差は、光干渉式膜厚測定装置（フィルメトリクス株式会社製、商品名：Ｆ８０）を用いて求めた。
　研磨速度（ＲＲ）＝（研磨前後での酸化珪素膜の膜厚差［ｎｍ］）／（研磨時間：１［ｍｉｎ］） The polishing rate (SiO 2 RR) of the silicon oxide film polished and washed under the above conditions was determined by the following equation. Table 1 shows the measurement results. The difference in thickness of the silicon oxide film before and after polishing was determined using an optical interference type film thickness measuring device (F80, manufactured by Filmetrics Co., Ltd.).
Polishing rate (RR) = (Difference in thickness of silicon oxide film before and after polishing [nm]) / (Polishing time: 1 [min])
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

Claims (8)

  1. 　砥粒及び液状媒体を含有するスラリであって、
    　前記砥粒が、金属酸化物及び金属水酸化物からなる群より選ばれる少なくとも一種の金属化合物を含み、
    　前記金属化合物が、複数の価数を取り得る金属を含み、
    　前記スラリが、当該スラリを被研磨面に接触させることにより前記砥粒を前記被研磨面に接触させたときに、前記金属の前記複数の価数の中で最も小さい価数の割合としてＸ線光電子分光法において０．１３以上を与える、スラリ。     A slurry containing abrasive grains and a liquid medium,
    The abrasive grains include at least one metal compound selected from the group consisting of metal oxides and metal hydroxides,
    The metal compound contains a metal capable of taking a plurality of valences,
    When the slurry is in contact with the surface to be polished by bringing the slurry into contact with the surface to be polished, X-rays as a ratio of the smallest valence among the plurality of valences of the metal. A slurry that gives 0.13 or more in photoelectron spectroscopy.
  2. 　前記最も小さい価数が３価である、請求項１に記載のスラリ。 The slurry of claim 1, wherein the smallest valence is trivalent.
  3. 　前記金属が希土類金属を含む、請求項１又は２に記載のスラリ。 The slurry according to claim 1 or 2, wherein the metal includes a rare earth metal.
  4. 　前記金属がセリウムを含む、請求項１～３のいずれか一項に記載のスラリ。 (4) The slurry according to any one of (1) to (3), wherein the metal includes cerium.
  5. 　前記スラリ中における前記砥粒のゼータ電位が＋１０ｍＶ以上である、請求項１～４のいずれか一項に記載のスラリ。 (5) The slurry according to any one of (1) to (4), wherein the zeta potential of the abrasive grains in the slurry is +10 mV or more.
  6. 　前記被研磨面が、珪素、アルミニウム、コバルト、銅、ガリウム、ゲルマニウム、ヒ素、ルテニウム、インジウム、スズ、ハフニウム、タリウム、タングステン及び白金からなる群より選ばれる少なくとも一種を含む、請求項１～５のいずれか一項に記載のスラリ。 The method according to claim 1, wherein the polished surface includes at least one selected from the group consisting of silicon, aluminum, cobalt, copper, gallium, germanium, arsenic, ruthenium, indium, tin, hafnium, thallium, tungsten, and platinum. A slurry according to any one of the preceding claims.
  7. 　砥粒及び液状媒体を含有するスラリを被研磨面に接触させることにより前記砥粒を前記被研磨面に接触させる工程と、
    　前記被研磨面に前記砥粒が接触した状態で、前記砥粒に含まれる金属の価数をＸ線光電子分光法により測定する測定工程と、を備え、
    　前記砥粒が、金属酸化物及び金属水酸化物からなる群より選ばれる少なくとも一種の金属化合物を含み、
    　前記金属化合物が、複数の価数を取り得る金属を含み、
    　前記測定工程において、前記金属の前記複数の価数の中で最も小さい価数の割合を得る、スラリのスクリーニング方法。     Contacting the abrasive grains with the surface to be polished by contacting the slurry containing the abrasive grains and the liquid medium with the surface to be polished,
    In the state where the abrasive grains are in contact with the surface to be polished, a measurement step of measuring the valence of metal contained in the abrasive grains by X-ray photoelectron spectroscopy,
    The abrasive grains include at least one metal compound selected from the group consisting of metal oxides and metal hydroxides,
    The metal compound contains a metal capable of taking a plurality of valences,
    A slurry screening method for obtaining the smallest valence ratio among the plurality of valences of the metal in the measuring step.
  8. 　請求項７に記載のスラリのスクリーニング方法の前記測定工程において得られる前記価数の割合として０．１３以上を与えるスラリを用いて前記被研磨面を研磨する工程を備える、研磨方法。 A polishing method, comprising a step of polishing the surface to be polished using a slurry that gives a valence ratio of 0.13 or more obtained in the measurement step of the slurry screening method according to claim 7.
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